Book of Abstracts - Enerchem-1
Transcript
Book of Abstracts - Enerchem-1
ENERCHEM 1 INTERDIVISIONAL GROUP ON CHEMISTRY FOR RENEWABLE ENERGY (ENERCHEM) ITALIAN CHEMICAL SOCIETY - 1st CONGRESS FIRENZE 18-20 FEBRUARY 2016 Book of Abstracts Published with the contribution of Section Toscana of the Italian Chemical Society (SCI) COMMITTEES SCIENTIFIC ADVISORY BOARD Alessandro Abbotto (President, Università degli Studi di Milano Bicocca) Catia Arbizzani (Università degli Studi di Bologna) Riccardo Basosi (Università degli Studi di Siena) Simona Binetti (Università degli Studi di Milano Bicocca) Paolo Fornasiero (Università degli Studi di Trieste) Gaetano Granozzi (Università degli Studi di Padova) Massimo Innocenti (Università degli Studi di Firenze) Mauro Marchetti (CNR-ICB Sassari) Michele Maggini (Università degli Studi di Padova) Mario Marchionna (ENI Saipem) Piercarlo Mustarelli (Università degli Studi di Pavia) Maurizio Peruzzini (CNR-ICCOM Sesto Fiorentino) Francesco Vizza (CNR-ICCOM Sesto Fiorentino) Lorenzo Zani (CNR-ICCOM, Sesto Fiorentino) ORGANIZING COMMITTEE Alessandro Mordini (Chairman, CNR-ICCOM Sesto Fiorentino) Massimo Innocenti (Co-chairman, Direttivo EnerCHEM, Università degli Studi di Firenze) Riccardo Basosi (Direttivo EnerCHEM, Università degli Studi di Siena) Massimo Calamante (Website master, CNR-ICCOM Sesto Fiorentino) Maurizio Peruzzini (Direttivo EnerCHEM, CNR-ICCOM Sesto Fiorentino) Gianna Reginato (secretary, CNR-ICCOM Sesto Fiorentino) Adalgisa Sinicropi (Website master, Università degli Studi di Siena) Francesco Vizza (CNR-ICCOM, Sesto Fiorentino) Lorenzo Zani (CNR-ICCOM, Sesto Fiorentino) Book editors: Antonella Guerriero, Massimo Calamante LOCAL ORGANIZERS Matteo Bartolini Matteo Bessi Enrico Berretti Ottavia Bettucci Andrea Comparini Antonio De Luca Alessio Dessi’ Bianca Cecconi Daniele Franchi Andrea Giaccherini Walter Giurlani Antonella Guerriero Maurizio Passaponti Francesca Russo SPONSORS UNDER THE PATRONAGE OF: AND WITH THE CONTRIBUTE OF: AND THE SUPPORT OF: SCIENTIFIC PROGRAMME THURSDAY, 18TH FEBRUARY 2016 (Centro Didattico Morgagni) 09:00-11:00 REGISTRATION 11:00-11:30 OPENING Chairperson: M. Maggini 11:30-12:10 PL1 - J. Durrant "Charge carrier dynamics for solar energy conversion" 12:10-12:40 KN1 - M. Bonchio "Small molecule activation for artificial photosynthesis" 12:40-14:00 LUNCH Chairperson: C. Arbizzani 14:00-14:30 KN2 - M. Wohlfahrt-Mehrens "Materials and process development for high energy lithium ion batteries" Session I; room 101. Chairperson: I. Rossetti 14:30-14:50 OP1 - V. Dal Santo "Optimization of Au nanoparticles decorated brookite TiO2 nanorods for photoelectrochemical water oxidation: bulk versus surface plasmonic decoration" 14:50-15:10 OP3 - M. Musiani "Electrodeposition and galvanic displacement: new routes to 3D catalysts for clean combustion and H2 electrolytic production" 15:10-15:30 OP5 - L. Calvillo "Fast one-pot synthesis of MoS2/crumpled graphene p−n nanonjuncDons for enhanced photoelectrochemical hydrogen production" 15:30-15:50 OP7 - L. Guidoni "Structure and catalytic mechanisms in water-splitting amorphous oxides” 15:50-16:10 OP9 - E. Rebollo "BaCe0.85-xZrxY0.15O3-d and Y- or Gd-doped CeO2 ceramic-ceramic composite membranes for hydrogen separation" 16:10-16:30 OP11 - M. Bruschi "[NiFe]-hydrogenases: a DFT investigation of the inactivation mechanisms under aerobic and anaerobic conditions" Session II; room 109. Chairperson: M. Innocenti 14:30-14:50 OP2 - C. Arbizzani "Energy storage and conversion systems: from Li-ion to Li-O2 batteries" 14:50-15:10 OP4 - S. Brutti "Surface reactivity of a carbonaceous cathode in Li-O2 cells" 15:10-15:30 OP6 - S. Santangelo "Electro-spin carbon-enriched cobaltosic oxide fibrous mats as binder-free electrode materials in flexible Li-ion batteries" 15:30-15:50 OP8 - R. Ruffo "Co3O4 anode material for Na-ion rechargeable batteries" 15:50-16:10 OP10 - M. A. Navarra "Novel liquid and polymer electrolytes for lithium-sulfur batteries" 16:10-16:30 OP12 - A. B. Muñoz-García "Rational design of triple conducting oxides from mixed ion-electron conductors: ab initio study of A-doped Sr2Fe1.5Mo0.5O6-δ" 16:30-17:20 BREAK/POSTER Session I; room 101. Chairperson: C. Arbizzani 17:20-17:40 OP13 - N. Manfredi "Thiophene-based phenothiazines for dye-sensitized solar cells and photocatalytic H2 production" 17:40-18:00 OP15 - L. Fagiolari "A ternary ZnAlIr layered hydroxide as efficient water oxidation heterogeneous catalyst" 18:00-18:20 OP17 - G. Valenti "Co-axial nanostructures for energy conversion: synergic effects between carbon nanotubes and metal oxides" 18:20-18:40 OP19 - A. Visibile “IInfluence of metallic under-layer in the performance of Cu2O photocathode & novel method for the investigation of photoactive semiconductor materials using cavity micro tips (C-ME) & SECM" 18:40-19:00 OP21 - G. Barbieri "Hydrogen upgrading with membrane reactors" 19:00-19:20 OP23 - L. Gonsalvi "Exploiting the HCOOH/CO2 cycle for hydrogen production and storage by homogeneous catalysis" Session II; room 109. Chairperson: L. Zani 17:20-17:40 OP14 - J. Amici "Nanostructured oxygen selective membrane for Li-air battery operating in ambient air" 17:40-18:00 OP16 - A. Giaccherini "Sustainable synthesis of pyrite nanoparticles for solar energy conversion and storage" 18:00-18:20 OP18 - L. Cupellini "Quantum chemical calculation of energy transfer and photoinduced electron transfer rates in donorbridge-acceptor systems" 18:20-18:40 OP20 - M. Baroncini "An artificial molecular pump powered by light energy" 18:40-19:00 OP22 - L. Baldini "Energy transfer studies in heterobichromophoric calixarene systems" 19:00-19:20 OP24 - M. Cacciarini "Second generation molecular switches based on dihydroazulene/ vinylheptafulvene" 19:30 WELCOME COCKTAIL FRIDAY, 19 FEBRUARY 2016 (Centro Didattico Morgagni) Chairperson: P. Mustarelli 09:00-9:30 KN3 - S. Campagna "Artificial photosynthesis: dendrimerbased self-assembling strategies for light harvesting and charge separation" Session I; room 101. Chairperson: P. Mustarelli 09:30-9:50 OP25 - S. Carli "A new 1,3,4-oxadiazole-based hole transport material for efficient CH3NH3PbBr3 perovskite solar cells: facile synthesis and energy level alignment" 09:50-10:10 OP27 - E. Menna "Chemical modification of carbon nanostructures for energy materials" 10:10-10:30 OP29 - A. Pucci "Luminescent solar concentrators: harnessing the benefits of new fluorophore/polymer matrix combinations" Session II; room 109. Chairperson: S. Bordiga 09:30-9:50 OP26 - A. Laganà "Virtual organizations at work: a plant for producing carbon neutral CH4" 09:50-10:10 OP28 - C. Nervi "New transition metal complexes for catalytic CO2 reduction" 10:10-10:30 OP30 - G. d'Ippolito "A chemical view at a sustainable process for bioenergy production" 10:30-11:20 BREAK/POSTER Session I; room 101. Chairperson: A. Sinicropi 11:20-11:40 OP31 - A. Dessì "Blue dyes for near-infrared absorbing dyesensitized solar cells" 11:40-12:00 OP33 - M. Magni "Bis-phenanthroline copper complexes in iodine-free electrolytes for DSSCs" 12:00-12:20 OP35 - I. Zama "Dye-sensitized solar cells: an example of a photoelectrochemical device in architecture" 12:20-12:40 OP37 - C. Barolo "Water-based electrolytes in hybrid solar cells: from liquid to gel formulations" Session II; room 109. Chairperson: M. Marchetti 11:20-11:40 OP32 - I. Rossetti "Electric and thermal energy from bioethanol: process intensification by using diluted feed" 11:40-12:00 OP34 - S. Cimino "Impact of sulphur on dry reforming of biogas over a Rh/Al2O3 catalyst" 12:00-12:20 OP36 - G. Torzillo "Biological constraints in the scale-up of photobiological hydrogen production" 12:20-12:40 OP38 - R. Rossi "Characterization of an yeast based Microbial Fuel Cell" 12:40-13:50 LUNCH Chairperson: G. Reginato 13:50-14:20 KN4 - G. Farinola "Photoconverters with organic semiconductors and photosynthetic bacteria" Session I; room 101. Chairperson: G. Reginato 14:20-14:40 OP39 - G. Marianetti "2,5-Diaryl substituted azoles as promising dyes for luminescent solar concentrators" 14:40-15:00 OP41 - A. Mucci "Conjugated polymers for solar cells incorporating the dithienosilole unit" 15:00-15:20 OP43 - S. Belviso "Thio-ethylporphyrazine nanohybrids with single-wall carbon nanotubes and graphene for photoinduced electron transfer" 15:20-15:40 OP45 - G. Di Carlo "β-Substituted porphyrinic dyes with tunable photoelectrochemical properties" Session II; room 109. Chairperson: F. Vizza 14:20-14:40 OP40 - H. Miller "Pd/C-CeO2 anode catalyst for high performance platinum free anion exchange membrane fuel cells" 14:40-15:00 OP42 - M. Longhi "Sugar-based iron-doped N-carbons for oxygen reduction reaction" 15:00-15:20 OP44 - I. Nicotera "Nanoscale ionic materials for advanced nanocomposites in high temperature proton exchange membrane fuel cells" 15:20-15:40 OP46 - V. di Noto "New materials for electrochemical energy conversion and storage" 15:40-16:40 BREAK/POSTER Session I; room 101. Chairperson: M. Peruzzini 16:40-17:00 OP47 - S. la Gatta "Garnishing the photosynthetic reaction center to improve performances" 17:00-17:20 OP49 - A. E. Di Mauro "Hybrid systems based on CdSe nanocrystals in low band gap copolymer for solar cells “ 17:20-17:40 OP51 - R. A. Picca "XPS surface characterization of electrochemically deposited semiconductors for photovoltaic applications" 17:40-18:00 OP53 - R. A. Mereu "Alternative buffer layers deposited by radio frequency sputtering for chalcogenide thin films solar cells" Session II; room 109. Chairperson: G. Granozzi 16:40-17:00 OP48 - G. Tuci "Chemically functionalized carbon nanotubes with pyridine groups as easily tunable N-decorated nanomaterials for the oxygen reduction reaction" 17:00-17:20 OP50 - C. Durante "Synergistically enhanced performances of Pt nanoparticles on doped mesoporous carbon for oxygen reduction reaction" 17:20-17:40 OP52 - C. Tealdi "Tailoring materials properties through defects and strain: the example of perovskite-type LaGaO3" 17:40-18:00 OP54 - V. Baglio "Cathode catalysts development for polymer electrolyte fuel cells" Chairperson: M. Peruzzini 18:00-18:30 KN5 - N. Armaroli "Solar electricity and solar fuels: status and perspectives in the context of the energy transition” 20:30 SOCIAL DINNER SATURDAY, 20 FEBRUARY 2016 (Auditorium Sant'Apollonia) Chairperson: A. Abbotto 09:00-9:40 PL2 - A. Hagfeldt "The versatility of mesoscopic solar cells" 09:40-10:10 KN6 - N. Alonso-Vante "Advanced electrode materials and evaluation in micro-fuel cells platform” 10:10-10:50 COFFEE BREAK 10:50-12:10 PANEL DISCUSSION “L'Energia in Italia dopo il COP21: sviluppo tecnologico delle rinnovabili e prospettive per la decarbonizzazione dell'economia” Moderatrice : Agnese Cecchini, Direttore Editoriale Gruppo Italia Energia Chairperson: S. Binetti 12:10-12:30 Poster award: flash presentation 12:30-13:00 AL - F. Bella "Photopolymers for stable solar cells, sodium batteries and photoelectrochromic windows" 13:00-13:30 CLOSING POSTER SECTION All the posters will be displayed during the whole meeting and discussed Thursday 18th from 15.50 to 16.40 and Friday 19th from 10.30 to 11.20 and from 15.50 to 16.40 P01 MESOPOROUS SILICA-BASED NAFION COMPOSITES MEMBRANES FOR APPLICATIONS IN SINGLE-CHAMBER MICROBIAL FUEL CELLS (MFC) Luca Millia, Simone Angioni, Gianna Bruni, Piercarlo Mustarelli, Eliana Quartarone P02 SOLID STATE NMR ANALYSIS OF SOLAR CELL MATERIALS Roberto Avolio, Antonio Abate, Maria Emanuela Errico P03 ELECTROCHEMISTRY OF THIOPHENE CONTAINING SENSITIZERS FOR DYE-SENSITIZED SOLAR CELLS ORGANIC Clara Baldoli, Lucia Viglianti, Alessandro Bolzoni, Alberto Bossi, Patrizia Romana Mussini, Emanuela Licandro P04 POLYMETHINE DYES AS NIR SENSITIZERS FOR DSCs Nadia Barbero, Simone Galliano, Davide Saccone, Claudia Barolo, Pierluigi Quagliotto, Guido Viscardi P05 NOVEL NON-AQUEOUS AMINE SOLVENTS FOR BIOGAS UPGRADING Francesco Barzagli, Fabrizio Mani, Maurizio Peruzzini P06 CARBON DIOXIDE UPTAKE AS AMMONIA AND AMINE CARBAMATES AND THEIR EFFICIENT CONVERSION INTO UREA AND 1,3DISUBSTITUTED UREAS Francesco Barzagli, Fabrizio Mani, Maurizio Peruzzini P07 HYPER FLEXIBLE DYE-SENSITIZED MICROFLUIDIC STABLE DEVICES SOLAR CELLS: TOWARDS Federico Bella, Andrea Lamberti, Stefano Bianco, Elena Tresso, Candido Fabrizio Pirri, Claudio Gerbaldi P08 ENERGY AND CHEMICALS FROM THE SELECTIVE ELECTROOXIDATION OF RENEWABLE DIOLS BY ORGANOMETALLIC FUEL CELLS (OMFCs) Marco Bellini, Maria Gelsomina Folliero, Maria Vincenza Pagliaro, Hamish Artur Miller, Jonathan Filippi, Alessandro Lavacchi, Andrea Marchionni, Werner Oberhauser, Francesco Vizza P09 ELECTROCHEMICAL ATOMIC LAYER DEPOSITION OF P & N SEMICONDUCTOR FILMS FOR PHOTOVOLTAIC APPLICATIONS Enrico Berretti, Francesco Di Benedetto, Nicola Cioffi, Ferdinando Capolupo, Alessandro Lavacchi, Rosaria Anna Picca, Andrea Comparini, Maurizio Passaponti, Massimo Innocenti P10 ELECTRODEPOSITION OF ALUMINIUM FOR GAS TURBINE APPLICATIONS: INFLUENCE OF THE BOND COAT DEPOSITION PARAMETERS ON THE CORROSION RESISTANCE Enrico Berretti, Andrea Giaccherini, Stefano Martinuzzi, Stefano Caporali, Massimo Innocenti P11 A RECHARGEABLE MAGNESIUM CHLOROALUMINATE IONIC LIQUIDS BATTERY BASED ON Federico Bertasi, Gioele Pagot, Keti Vezzù, Enrico Negro, Graeme Nawn, Antoine Bach Delpeuch, Riccardo Rigato, Sara Tonello, Giuseppe Pace, Vito Di Noto P12 STUDY OF SWIRL SHAPED DEFECTS IN HIGH EFFICIENCY N-TYPE SILICON SOLAR CELLS Simona Binetti, Alessia Le Donne, Valerio Folegatti, Gianluca Coletti P13 DYE-SENSITIZED SOLAR CELLS BASED ON WATER-BASED ECOFRIENDLY NATURE-INSPIRED DEEP EUTECTIC SOLVENT ELECTROLYTE SOLUTIONS Chiara Liliana Boldrini, Norberto Manfredi, Filippo M. Perna, Vito Capriati, Alessandro Abbotto P14 INVESTIGATION OF THE PROMOTING EFFECT OF Mn IN STEAM AND AQUEOUS PHASE REFORMING OF GLYCEROL OVER Pt-Mn/C CATALYST Filippo Bossola, Vladimiro Dal Santo, Sandro Recchia, Junming Sun, Yong Wang P15 Pt3Y ALLOY SYNTHESIS ON MESOPOROUS CARBON SUPPORT Riccardo Brandiele, Christian Durante, Emilia Grądzka, Jian Zheng, Gian Andrea Rizzi, Gaetano Granozzi, Armando Gennaro P16 STRUCTURAL AND MORPHOLOGICAL TUNING OF LiCoPO4 MATERIALS SYNTHESIZED BY SOLVO-THERMAL METHODS FOR Li-CELL APPLICATIONS Jessica Manzi, Mariangela Curcio, Sergio Brutti P17 OPERANDO ELECTROCHEMICAL NMR MICROSCOPY OF POLYMER FUEL CELLS Alice S. Cattaneo, Davide C. Villa, Simone Angioni,Chiara Ferrara, Roberto Melzi, Eliana Quartarone, Piercarlo Mustarelli P18 SYNTHESIS AND CHARACTERIZATION OF CROCONAINE DYES, A PROMISING CLASS OF NIR SENSITIZERS Cosimo Vincenzo Ciasca, Vincenzo Fino, Maria Annunziata Capozzi, Angela Punzi, Ambra Fiore, Davide Vurro, Gianluca Maria Farinola P19 INNOVATIVE AND FUNCTIONAL MATERIALS FOR GREEN AND SAFE NaION LARGE-SCALE ENERGY STORAGE Francesca Colò, Giuseppina Meligrana, Jijeesh R. Nair, Federico Bella, Andrea Lamberti, Matteo Destro, Sonia Fiorilli, Paolo P. Pescarmona, Claudio Gerbaldi P20 STEAM REFORMING OF CRUDE BIO-ETHANOL FOR HYDROGEN PRODUCTION OVER FP CATALYSTS Matteo Compagnoni, Josè Lasso, Alessandro Di Michele, Ilenia Rossetti P21 ELECTRODEPOSITION AND CHARACTERIZATION OF THIN FILMS OF MoS2 Andrea Comparini, Ferdinando Capolupo, Andrea Giaccherin, Maurizio Passaponti, Francesco Di Benedetto, Alessandro Lavacchi, Emanuele Piciollo, Massimo Cavallini, Massimo Innocenti P22 SYNTHESIS AND PHOTOCHEMICAL PROPERTIES OF NEW MELANININSPIRED ELECTROLUMINESCENT MATERIALS FOR OLED APPLICATIONS Valeria Criscuolo, Paola Manini, Alessandro Pezzella, Pasqualino Maddalena, Salvatore Aprano, Maria Grazia Maglione, Paolo Tassini, Carla Minarini, Marco d’Ischia P23 SPLIT WITH RUST! MODIFIED HEMATITE PHOTOANODES FOR SOLAR WATER SPLITTING Nicola Dalle Carbonare, Roberto Argazzi, Stefano Caramori, Carlo Alberto Bignozzi P24 EFFICIENT PHOTOINDUCED CHARGE SEPARATION IN A BODIPY-C60 DYAD Alessandro Iagatti, Paolo Foggi, Laura Bussotti, Stefano Cicchi, Stefano Fedeli, Giacomo Biagiotti, Massimo Marcaccio, Eleonora Ussano, Benedetta Mennucci, Lorenzo Cupellini, Stefano Caprasecca, Mariangela Di Donato P25 BICHROMOPHORIC CALIX[4]ARENE BASED SYSTEM FOR THE STUDY OF PHOTOINDUCED ELECTRON TRANSFER Federica Faroldi, Aurora Sesenna, Irene Tosi,aLaura Baldini, Francesco Sansone P26 PHOTOCATALYTIC ACTVITY OF NP-TIO2 SUPPORTED ON A NEW PERSISTENT LUMINESCENCE PHOSPHOR Maurizio Ferretti, Federico Locardi, Giorgio Andrea Costa, Stefano Alberti, Ilaria Nelli, Valentina Caratto, Elisa Sanguineti, Marco Fasoli, Marco Martini P27 PLASMONIC TiO2 THIN FILMS: INTERACTION BETWEEN NANOPARTICLES AND ORGANIC DYES FOR DSSC APPLICATIONS Au Daniele Franchi, Bengt-Erik Mellander, Maurizio Furlani, Valeria Saavedra Becerril, Massimo Calamante, Alessandro Mordini, Gianna Reginato, Lorenzo Zani P28 PEROVSKITE SOLAR CELLS STABILIZED BY CARBON NANOSTRUCTURESP3HT BLENDS Simone Casaluci, Teresa Gatti, Francesco Bonaccorso, Enzo Menna, Aldo Di Carlo P29 NEW POLYMERIC SINGLE-ION CONDUCTORS FOR RECHARGEABLE LITHIUM BATTERIES Luca Porcarelli, Alexander S. Shaplov, Maitane Salsamendi, Jijeesh R. Nair, Federico Bella, Yakov S. Vygodskii, David Mecerreyes, Claudio Gerbaldi P30 A SIMPLE ROUTE TOWARDS NEXT-GEN GREEN ENERGY STORAGE BY FIBRE-BASED SELF-SUPPORTING ELECTRODES AND A TRULY SOLID POLYMER ELECTROLYTE Lorenzo Zolin, Jijeesh R. Nair, Federico Bella, Giuseppina Meligrana, Pravin V. Jagdale, Irene Cannavaro, Alberto Tagliaferro, Didier Chaussy, Davide Beneventi, Claudio Gerbaldi P31 IN-SITU SXRD STUDY OF THE E-ALD ELECTRODEPOSITION PROCESS OF Cu-S ULTRA-THIN FILMS SEMICONDUCTOR FOR SOLAR ENERGY CONVERSION Andrea Giaccherini, Rosaria Anna Picca, Maria Chiara Sportelli, Ferdinando Capolupo, Giordano Montegrossi, Nicola Cioffi, Roberto Felici, Francesco Carlà, Alessandro Lavacchi, Francesco Di Benedetto, Massimo Innocenti P32 BAND GAP REVISED: A COMPUTATIONAL STUDY OF STRUCTURALLY RELATED POLY-THIOPHENES FOR PHOTOVOLTAICS Davide Vanossi, Luigi Cigarini, Andrea Giaccherini, Massimo Innocenti, Claudio Fontanesi P33 OIL PRODUCTION AS A DYNAMICAL SYSTEM L. Celi, C. Della Volpe, S. Siboni, L. Battisti, L. Pardi P34 FIXED ENERGY X-RAY ABSORPTION VOLTAMMETRY FOR INVESTIGATION OF REACTION MECHANISM IN ALKALINE DIRECT ALCOHOL FUEL CELLS W. Giurlani, A. Lavacchi, C. Zafferoni, A. Giaccherini, A. De Luca, G. Montegrossi, F. Di Benedetto, F. d'Acapito, M. Innocenti P35 EFFECT OF TRIALKOXYSILANE GROUP LINKER ON PHOTOINDUCED CHARGE INJECTION ON TIO2 NANOSTRUCTURED FILMS Alessandro Iagatti, Mariangela Di Donato, Sandra Doria, Marco Monini, Daniele Franchi, Massimo Calamante, Lorenzo Zani, Adalgisa Sinicropi, Gianna Reginato, Paolo Foggi P36 MANGANESE COMPLEXES AS REDOX MEDIATORS IN DYE SENSITIZED SOLAR CELLS Stefano Carli, Elisabetta Benazzi, Laura Casarin, Stefano Caramori, Roberto Argazzi, Carlo Alberto Bignozzi P37 MATERIALS AND METHODS FOR ENERGY HARVESTING IN THE SHOES INDUSTRY Fabio Invernizzi, Leonardo Lanfredi, Maddalena Patrini, Sergio Dulio, Piercarlo Mustarelli P38 A POLARIZABLE QM/CLASSICAL APPROACH FOR THE MODELLING OF ELECTRONIC ENERGY TRANSFER IN EMBEDDED SYSTEMS Sandro Jurinovich, Benedetta Mennucci P39 ELECTROSPUN HYBRID GEL POLYMER ELECTROLYTE FOR LITHIUM BATTERIES Catia Arbizzani, Francesca De Giorgio, Davide Fabiani, Maria Letizia Focarete, Andrea La Monaca, Marco Zaccaria P40 INTEGRATED POWER TO GAS PROCESSES: TECHNICAL AND ECONOMICAL FEASIBILITY Grazia Leonzio P41 ENVIROMENTAL ANALYSIS OF PROCESSES TO PRODUCE BIO-METHANE Grazia Leonzio P42 SUITABLE ENVIRONMENTAL REFRIGERATION FOR PHOTOVOLTAIC/ THERMAL SYSTEM IN DUBAI Grazia Leonzio P43 MODELING OF PHOTOVOLTAIC/THERMAL SOLAR PANEL Grazia Leonzio P44 SUPPRESSION OF OPTICAL BANDGAP RECOMBINATION IN PHOTODEPOSITED NiOX-COATED HEMATITE ELECTRODES FOR WATER SPLITTING APPLICATION F. Malara, F. Fabbri, M. Marelli, V. Dal Santo, R. Psaro, A. Naldoni P45 A NOVEL ENVIRONMENTALLY FRIENDLY 3-V Na-ION CELL Jessica Manzi, Sergio Brutti P46 COMPARATIVE LCA OF A BIPV APPLICATION: AMORPHOUS SILICON VS DYE SENSITIZED SOLAR WINDOWS Simone Maranghi, Maria Laura Parisi, Adalgisa Sinicropi, Riccardo Basosi P47 Cu2MnSnS4: AN ALTERNATIVE CHALCOGENIDE TO PUSH THE PV ON TWSCALE Stefano Marchionna, Federico Cernuschi, Alessia Le Donne, Simona Binetti, Maurizio Acciarri, Marco Merlini P48 LiBH4/ZrCoH3 DOPING EFFECT ON THE H2 STORAGE KINETICS OF LiNH2MgH2 COMPLEX HYDRIDE Alessio Masala, Jenny G. Vitillo, Silvia Bordiga and Marcello Baricco P49 CONCENTRATION OF VINASSE BY PHYSICOCHEMICAL PROCESSES, USING FERRIC SULFATE P. Sica; A. S. Baptista; C. L. Aguiar; R. S. Carvalho; M. Silverio; R. P. Calegari; F. C. Tonoli; A. Trevizan; M. Outeiro; E. M. Carvalho; J. P. Neto P50 CONCENTRATION OF VINASSE BY PHYSICOCHEMICAL PROCESSES USING ALUMINUM SULFATE. P. Sica; A. S. Baptista; C. L. Aguiar; R. S. Carvalho; M. Silverio; R. P. Calegari; F. C. Tonoli; A. Trevizan; M. Outeiro; E. M. Carvalho; J. P. Neto P51 PRODUCTION OF BIOENERGY FROM BYPRODUCT OF SUGARCANE MILL P. Sica; A. S. Baptista; C. L. Aguiar, K. C. Das; J. P. Neto P52 SCREENING AND STUDY OF LOW-COST OER PHOTOELECTROCATALYSTS BY SCANNING ELECTROCHEMICAL MICROSCOPY (SECM) Sara Morandi, Alberto Naldoni, Cristina Locatelli, Francesco Malara, Vladimiro Dal Santo, Alberto Vertova, Sandra Rondinini, Alessandro Minguzzi P53 NEW INSIGHTS TOWARDS AGING RESISTANT LITHIUM POLYMER BATTERIES FOR WIDE TEMPERATURE APPLICATIONS Jijeesh R Nair, Luca Porcarelli, Federico Bella, Rongying Lin, Sebastien Fantini, Giovanna Maresca, Margherita Moreno, Giovanni B. Appetecchi, Claudio Gerbaldi P54 SILICON-DRIVEN MORPHOLOGY, STRUCTURE, AND WATER SPLITTING ACTIVITY IN HEMATITE NANOSTRUCTURES Francesco Malara, Mattia Allieta, Marcello Marelli, Saveria Santangelo, Salvatore Patane, Claudia Triolo, Rinaldo Psaro, Vladimiro Dal Santo, Alberto Naldoni P55 NEW PHOTOACTIVE MATERIALS BASED ON DOPED ZrO2 M.C. Paganini, Chiara Gionco, Elio Giamello P56 EFFECTS OF Ni/Co DOPING ON THE PROPERTIES OF LiFeαNiβCoγPO4 CATHODES FOR LITHIUM BATTERIES Gioele Pagot, Federico Bertasi, Graeme Nawn, Enrico Negro, Giuseppe Pace, Stefano Polizzi, Vito Di Noto P57 DINUCLEAR TRICARBONYL RE(I) COMPLEXES: ELECTROCATALYTIC SYSTEMS FOR CO2 REDUCTION NEW EFFICIENT Elsa Quartapelle Procopio, Monica Panigati, Alessandro Boni, Pierluigi Mercandelli, Giovanni Valenti, Francesco Paolucci P58 A NEW SEMI-SOLID, FLOW Li/O2 BATTERY Irene Ruggeri, Catia Arbizzani, Francesca Soavi P59 NOVEL ORGANIC DYES IN PHOTOELECTROCHEMICAL SYSTEMS Federica Sabuzi, Emanuela Gatto, Mariano Venanzi, Barbara Floris, Valeria Conte, Pierluca Galloni P60 HIGHLY POROUS ELECTROSPUN HEMATITE PHOTOELECTROCHEMICAL WATER SPLITTING FIBRES FOR Saveria Santangelo, Patrizia Frontera, Fabiola Pantò, Alberto Naldoni, Francesco Malara, Marcello Marelli, Vladimiro Dal Santo, Salvatore Patané, Claudia Triolo, Pierluigi Antonucci P61 INTERMEDIATE TEMPERATURE SOFC FED BY BIOGAS: EXTERNAL REFORMER DEVELOPMENT Caterina Sarno, Igor Luisetto, Simonetta Tuti, Silvia Licoccia, Elisabetta Di Bartolomeo P62 IN SILICO DESIGN OF NEW SENSITIZERS FOR TYPE II DSSC Adalgisa Sinicropi, Maria Laura Parisi, Gianna Reginato, Lorenzo Zani,b Massimo Calamante, Alessandro Mordini, Riccardo Basosi, Maurizio Taddei P63 PERFORMANCE OF PEM ELECTROLYSIS MEAs BASED ON ADVANCED ELECTROCATALYSTS AND MEMBRANE Stefania Siracusano, Vincenzo Baglio, Eddy Moukheiber, Luca Merlo, Antonino Salvatore Arico’ P64 POLY(CYANOVINYLENE PHENYLENE-CO-THIOPHENE)S FOR POLYMER SOLAR CELLS Francesco Tassinari, Francesca Parenti, Francesco Paolo Di Nicola, Barbara Ballarin, Massimiliano Lanzi, Emanuela Libertini, Adele Mucci P65 EFFECT OF THE PREPARATION METHOD ON THE ELECTROCHEMICAL PROPERTIES OF PYROPHOSPHATE-BASED CATHODES FOR RECHARGEABLE Na-ION BATTERIES Cristina Tealdi, Monica Ricci, Chiara Ferrara, Giovanna Bruni, Eliana Quartarone, Piercarlo Mustarelli P66 Pd-Au CATALYST FOR THE HYDROGENATION OF LEVULINIC ACID TO γ−VALEROLACTONE γ− AT MILD CONDITION Maria Luisa Testa, Valeria La Parola Anna Maria Venezia P67 WO3 NANOROLLS SELF-ASSEMBLED AS THIN FILMS BY HYDROTHERMAL SYNTHESIS: A VERSATILE MATERIAL FOR ELECTRO-OPTICAL APPLICATIONS. Svetoslava Vankova, Simone Zanarini, Julia Amici, Nerino Penazzi, Silvia Bodoardo P68 COMMERCIAL ALUMINUM ALLOY AS ANODE FOR Li-ION BATTERIES Svetoslava Vankova, Roberto Doglione, Nerino Penazzi, Silvia Bodoardo P69 TRIARYLAMINE-BASED HYDRIDO-CARBOXYLATE RHENIUM(I) COMPLEXES AS PHOTOSENSITIZERS FOR DYE-SENSITIZED SOLAR CELLS Lorenzo Veronese, Elsa Quartapelle, Pierluigi Mercandelli, Thomas Moehl, Monica Panigati, Anders Hagfeldt P70 ANODIC MATERIALS FOR LITHIUM-ION COMPOSITES FOR HIGHPOWER APPLICATIONS. BATTERIES: TIO2-rGO Daniele Versaci, Marco Minella, Claudio Minero, Carlotta Francia, Silvia Bodoardo, Nerino Penazzi P71 EFFICIENCY ENHANCEMENT BY CATION EFFECT IN DSSC WITH PAN BASED GEL POLIMER ELECTROLYTES Ottavia Bettucci, Massimo Calamante, Alessandro Mordini, Lorenzo Zani, Gianna Reginato, Murizio Peruzzini, T.M.W.J. Bandara, Valeria Saavedra, Maurizio Furlani, Bengt Erik Mellander P72 DESIGN AND SYNTHESIS OF PHOTOSENSITIZERS WITH ALKOXYSILANE ANCHORING GROUPS FOR NEW GENERATION SOLAR CELLS Matteo Bessi, Marco Monini, Massimo Calamante, Alessandro Mordini, Adalgisa Sinicropi, Mariangela Di Donato, Alessandro Iagatti, Paolo Foggi, Lorenzo Zani, Gianna Reginato P73 DRIVING THE SELECTIVITY OF ELECTROCHEMICAL CO2 REDUCTION TO FORMIC ACID: SYNERGIC EFFECTS IN A C-BASED HETEROSTRUCTURE Boni A., Valenti G., Montini T., Fornasiero P., Prato M. and Paolucci F. P74 SYNTHESIS OF NEW 1-PHENYLPYRROLE BASED MOLECULES FOR DYESENSITIZED SOLAR CELLS Tamás Hergert, Béla Mátravölgyi, Angelika Thurner, Alessandro Mordini, Ferenc Faigl P75 PHOTOCATALYTIC HYDROGEN PRODUCTION MATERIALS AND DEVICES Gian Luca Chiarello, Maria Vittoria Dozzi, Elena Selli P76 BIOFUELS FROM URBAN SEWAGE SLUDGE: A NEW EFFICIENT AND SUSTAINABLE PROCESS TO TURN WASTE INTO A NEW FEEDSTOCK Carlo Pastore, Luigi di Bitonto, Giuseppe Mascolo P77 VALORIZATION OF POLYSTYRENE WASTE FOAM AS POLYMER/CLAY NANOCOMPOSITE: APPLICATION AS METHANOL FUEL CELL MEMBRANE Stouri.Mbarek, Bekri.Imen, Srasra.Ezzedine P78 NANOCOMPOSITE MEMBRANES BASED ON PBI AND ZrO2 FOR HTPEMFCS Keti Vezzù, Graeme Nawn, Enrico Negro, Federico Bertasi, Giuseppe Pace, Antoine Bach Delpeuch, Gioele Pagot, Yannick Herve Bang, Chuanyu Sun, Vito Di Noto P79 A SELF-POWERED SUPERCAPACITIVE MICROBIAL FUEL CELL Carlo Santoro, Alexey Serov, Plamen Atanassov, Catia Arbizzani, Francesca Soavi P80 DYE-SENSITIZED PHOTOCATALYTIC H2 PRODUCTION: ENHANCED ACTIVITY IN A GLUCOSE DERIVATIVE OF A PHENOTHIAZINE DYE Bianca Cecconi, Norberto Manfredi, Riccardo Ruffo, Valentina Calabrese, Alberto Minotti, Francesco Peri, Tiziano Montini, Paolo Fornasiero, Alessandro Abbotto, P81 NEW SYNTHETIC STRATEGIES FOR INCORPORATION OF FLUOROPHORES INTO SAPONITE Valentina Toson, Claudia Barolo, Enrico Boccaleri, Diego Antonioli, Valentina Gianotti, Marco Milanesio. P82 ABSTRACTS Plenary Lectures (PL01-PL02) Keynote Lectures (KN01-KN06) Award Lecture (AL) Oral Presentations (OP01-OP54) Posters (P01-P82) 1 | PL01 CHARGE CARRIER DYNAMICS FOR SOLAR ENERGY CONVERSION James R Durrant Department of Chemistry, Imperial College London, London SW7 2AZ, U.K. and SPECIFIC IKC, College of Engineering, University of Swansea, Swansea, U.K. email: [email protected] The development of low cost, stable and efficient materials for solar energy conversion is a key scientific challenge for addressing global sustainability and energy supply. My talk will address focus on the charge carrier dynamics which play a key role in determining the efficiency of many of the developing solar energy technologies. I will focus on two technologies – organic solar cells based on polymer / fullerene blends for solar to electric power conversion, and metal oxide nanoparticles and photoelectodes for solar driven fuel synthesis. In my talk, I will also draw upon lessons we can learn from our understanding of the processes of charge separation and utilization in natural photosynthesis. For organic solar cells, I focus on the processes of photoinduced charge separation and recombination between donor polymers and acceptor small molecules. In particular I will address the impact of material energetics, crystallinity and nanostructure on these dynamics.1 For the metal oxides, I will address the timescales of charge separation and recombination, and in particular the kinetics of water splitting into molecular hydrogen and oxygen at the metal oxide / electrolyte interface.2,3 In both cases, I will discuss what lessons can be learnt about the materials design to enhance device performance, and the practical opportunities for technology development. References [1] Dimitrov, S. D., and Durrant, J. R. Materials Design Considerations for Charge Generation in Organic Solar Cells, Chemistry of Materials, 2014, 26, 616-630. [2] Dimitrov, S. D., Wheeler, S., Niedzialek, D., Schroeder, B. C., Utzat, H., Frost, J. M., Yao, J. Z., Gillett, A., Tuladhar, P. S., McCulloch, I., Nelson, J., Durrant, J. R. Polaron pair mediated triplet generation in polymer/fullerene blends, Nature Communications 2015, 6. [3] Barroso, M., Pendlebury, S. R., Cowan, A. J., and Durrant, J. R. Charge carrier trapping, recombination and transfer in hematite (alpha-Fe2O3) water splitting photoanodes, Chemical Science, 2013, 4, 2724-2734. [4] Tachibana, Y., Vayssieres, L., and Durrant, J. R. Artificial photosynthesis for solar watersplitting, Nature Photonics 2012, 6, 511-518 PL02 | 2 THE VERSATILITY OF MESOSCOPIC SOLAR CELLS Anders Hagfeldt Laboratory of Photomolecular Science, Swiss Federal Institute of Technology Lausanne (EPFL), CH1015, Lausanne, Switzerland email:[email protected] In our work on solid-state dye-sensitized solar cells (ssDSSC) we have recently [1] shown that copper phenanthroline complexes can act as an efficient hole transporting material. We prepared ssDSCs with the organic dye LEG4 and copper(I/II)phenantroline as redox system and achieved power conversion efficiencies of more than 8%. For perovskite solar cells (PSC) our best performance is presently achieved with a mixed composition of iodide/bromide and methyl ammonium/formamidinium [2]. We will report on our work on optimizing the solar cell efficiency that at present shows a certified world record efficiency of 21.0%. With the use of an ALD deposited SnO2 compact underlayer we have constructed a planar perovskite solar cell with a hysteresis free efficiency of above 18% [3]. Based on this configuration we have in collaboration with the group of Prof. Bernd Rech, Helmholtz Zentrum Berlin, prepared a monolithic Perovskite/Silicon-Heterojunction tandem solar cell with an efficiency above 18% [4], pointing out a promising direction for further improvement of tandem cells using PSCs as one of the constituents. Another possibility for a tandem system has been investigated in collaboration with Prof. Segawa and co-workers in which a spectral split-cell, using a combination of a DSSC cell (with a wideband dye DX3) and a perovskite cell, demonstrated an efficiency of 21.5% [5]. References [1] Freitag et al., Energy & Envir. Sci., DOI: 10.1039/C5EE1204J [2] Bi et al., Science Advance, accepted [3] Correa et al., Energy & Envir. Sci., DOI:10.1039/C5EE02608C [4] Albrect et al., Energy & Envir. Sci., DOI: 10.1039/C5EE02965A [5] Kinoshita et al., Nature Comm. DOI: 10.1038/ncomms9834 3 | KN01 SMALL MOLECULE ACTIVATION FOR ARTIFICIAL PHOTOSYNTHESIS Marcella Bonchio University of Padova and ITM-CNR UoS-PD, via Marzolo 1, Padova, Italy e-mail: [email protected] The artificial “off-leaf” transposition of Photosynthesis, is a dream-goal of energy research, aiming at the continuous production of hydrogen as solar fuel, from the photo-catalytic splitting of H2O.1 A recently discovered pathway has been carved at the interface of specifically tailored carbon nano-structures powering an efficient class of molecular catalysts. These latter display a unique mimicry of the Photosynthetic II enzyme.2 The shaping of their functions on carbon nano-surfaces opens a vast scenario for tuning electron/proton transfer mechanisms in term of rates, distance, geometries and communication between donor/acceptor centers.3,4 References [1] Al-Oweini, R.; Sartorel, A.; Bassil, B. S.; Natali, M.; Berardi, S.; Scandola, F.; Kortz, U.; Bonchio, M. Angew. Chem. Int. Ed., 2014.,126, 11364-11367.; Piccinin, S.; Sartorel, A.; Aquilanti, G.; Goldoni, A.; Bonchio, M.; Fabris, S. PNAS 2013, 110, 4917-4922 [2] Sartorel, A.; Bonchio, M.; Campagna, S.; Scandola, F. Chem. Soc. Rev. 2013, 42, 22622280 [3] Paolucci, F.; Prato, M.; Bonchio, M. et al. ACS Nano 2013, 7, 811; Paolucci, F.; Prato, M.; Bonchio, M. et al. Nature Chem. 2010, 2, 826-831. [4] Squarcina, A.; Fortunati, I.; Saoncella, O.; Galiano, F.; Ferrante, C.; Figoli, A.; Carraro, M.; Bonchio, M. Adv. Mater. Interfaces 2015, 2, DOI: 10.1002/admi.201500034. KN 02 | 4 MATERIALS AND PROCESS DEVELOPMENT FOR HIGH ENERGY LITHIUM ION BATTERIES Margret Wohlfahrt-Mehrens ZSW – Zentrum für Sonnenenergie- und Wasserstoff-Forschung, Baden-Württemberg, Helmholtzstrasse 8, D-89081 Ulm email:[email protected] Long life, efficient and safe high energy storage systems are the key components for hybrid and full electric cars as well as for intermediate storage of renewable energy sources. The lithium ion battery is the most promising system for these applications. The performance of lithium ion batteries has been constantly improved during the last twenty years. However, present lithium ion technology does not fulfill completely the requirements in terms of energy density and cost. In the past the increase of energy density has mainly been achieved by optimization of electrode microstructure and cell design and not by introducing new active materials. It is expected that the development of new active materials on both anode and cathode side can lead to further improvement of energy density and can also lead to significant cost reduction of complete batteries. Novel batteries beyond lithium technology like all solid state batteries, Lithium/Sulfur or Metal/Air batteries are very promising high energy candidates for the long range future. The presentation will summarize the state of the art of lithium ion batteries and beyond lithium battery systems. Ongoing research and development efforts for new active materials will be presented and discussed in detail. Further improvements of electrode and cell design and their impact on process and production technology will also be introduced. 5 | KN03 ARTIFICIAL PHOTOSYNTHESIS: DENDRIMER-BASED SELFASSEMBLING STRATEGIES FOR LIGHT HARVESTING AND CHARGE SEPARATION Fausto Puntoriero, Giuseppina La Ganga, Francesco Nastasi, Sebastiano Campagna* Dipartimento di Scienze Chimiche, Università di Messina, and Centro di Ricerca Interuniversitario per la Fotosintesi Artificiale (SOLARCHEM), sezione di Messina, Messina, Italy . e-mail: [email protected] Conversion of solar energy into fuels (artificial photosynthesis) is one of the Holy Grail of Science. Solution of this complex problem is quite appealing, as it could alleviate the huge energy problems which our society is going to face. Artificial photosynthesis, according to a bio-mimetic approach, requires the design of several components, each of them a supramolecular system, structurally organized and functionally integrated. Indeed, in analogy with the natural photosynthetic systems, in such integrated assemblies, photons and electrons have to be elaborated in a well-organized fashion, and all the process must be orchestrated in terms of space, energy, and time. Here we present some recent results obtained by our group related to (i) artificial lightharvesting antenna systems (their role: absorbing light and converting it into electronic energy, which can be funnelled to specific sites of the assemblies); (ii) charge separation systems (role: to use the electronic energy collected by the antennae to perform charge separation, that is to transform electronic energy into redox energy); (iii) integrated antenna and catalysts for water oxidation. References [1] F. Puntoriero, A. Sartorel, M. Orlandi, G. La Ganga, S. Serroni, M. Bonchio, F. Scandola, S. Campagna, Coord. Chem. Rev., 2011, 255, 2594. [2] M. Natali, S. Campagna, F. Scandola, Chem. Soc. Rev. 2014, 43, 4005. [3] M. Natali, F. Puntoriero, C. Chiorboli, G. La Ganga, A. Sartorel, M. Bonchio, S. Campagna, F. Scandola, J. Phys. Chem. C, 2015, 119, 2371. KN04 | 6 PHOTOCONVERTERS WITH ORGANIC SEMICONDUCTORS AND PHOTOSYNTHETIC BACTERIA Gianluca M. Farinola,*a Alessandra Operamolla,a Rocco R. Tangorra,a Francesco Milano,b Angela Agostiano,a,b Niyazi S. Sariciftci,c Eric D. Głowacki,c Massimo Trottab a Dipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Bari, Italy. CNR IPCF UOS BARI Dipartimento di Chimica Università degli Studi di Bari “Aldo Moro”, Bari, Italy. c Linz Institute for Organic Solar Cells (LIOS), Johannes Kepler University, Linz, Austria. b e-mail: [email protected] Photosynthetic Reaction Centers (RCs) are photoenzymes capable to convert solar energy into charge separated states with efficiency close to 100%. The possibility of taking advantage of this unmatched efficiency to create bio-hybrid photoconverters is very attractive.1 The lecture will present highly selective covalent functionalization of the RC from the photosynthetic bacterium Rhodobacter sphaeroides R26 with tailored molecular fluorophores which act as antennas to enhance the light harvesting capability of the RC in wavelength ranges where the unmodified enzyme does not absorb. As a result, the hybrid systems outperform the native protein in the photogeneration of charges and in the photoenzymatic activity.2 We have also demonstrated chemical modification for anchoring the RC on thin films of molecular semiconductors, obtaining an RC-sensitized photoconductor device operating in aqueous-environment.3 Our study discloses new concepts for the generation of bio-hybrid supramolecular materials for sunlight photoconversion from the combination of highly efficient photoactive natural structures, optimized in billions of years of evolution, with tailored functional molecules. References [1] Operamolla, A.; Ragni, R.; Milano, F.; Tangorra, R. R.; Antonucci, A.; Agostiano, A.; Trotta, M.; Farinola, G. M. J. Mater. Chem. C 2015, 3, 6471. [2] Milano, F.; Tangorra, R. R.; Hassan Omar, O.; Ragni, R.; Operamolla, A.; Agostiano, A.; Farinola, G. M.; Trotta, M. Angew. Chem. Int. Ed. 2012, 51, 11019. [3] Głowacki, E. D.; Tangorra, R. R.; Coskun, H.; Farka, D.; Operamolla, A.; Kanbur, Y.; Milano, F.; Giotta, L.; Farinola, G. M.; Sariciftci, N. S. J. Mater. Chem. C, 2015, 3, 6554. 7 | KN05 SOLAR ELECTRICITY AND SOLAR FUELS: STATUS AND PERSPECTIVES IN THE CONTEXT OF THE ENERGY TRANSITION Nicola Armaroli Consiglio Nazionale delle Ricerche, Istituto per la Sintesi Organica e la Fotoreattività, (CNR-ISOF), Via Gobetti 101, 40129 Bologna, Italy e-mail: [email protected] The energy transition from fossil fuels to renewables is already ongoing, but it will be a long, complex and difficult process to carry out, since the global energy system is a gigantic and complex machine. Key renewable energy production data will be discussed, which show the remarkable growth of solar electricity technologies and indicate that crystalline silicon PV and wind turbines are the workhorse of the first wave of renewable energy deployment on the TW scale around the globe. The PV market alternatives along with other less mature options under intensive research will be briefly presented, along with the perspectives of concentrated solar power options. As far as fuels are concerned, the situation is significantly more complex because making chemicals with sunshine is far more complicated than generating electric current. The prime solar artificial fuel is molecular hydrogen, which is characterized by an excellent combination of chemical and physical properties. The routes to make it via solar energy and then synthetic liquid fuels are presented. The interconversion between electricity and hydrogen, two energy carriers directly produced by sunlight, will be a key tool to distribute renewable energies with the highest flexibility. However, the full integration of solar hydrogen in the world energy system can be achieved only in the long term. Two parameters and concepts that are often neglected in the scientific energy debate will be highlighted: the EROI (Energy Return On Investment) and the fact that the energy transition will not be limited by the availability of photons, but by the availability of natural resources – particularly minerals – which are needed to manufacture energy converters and storage devices on a multi-TW scale. References [1] Armaroli, N.; Balzani V. Chem. Eur. J. 2016, 22, DOI: 10.1002/chem.201503580 [2] Armaroli, N.; Balzani V. Energy for a Sustainable World. From the Oil Age to a Sun Powered Future, Wiley-VCH, 2011. [3] Armaroli, N.; Balzani V., Serpone N. Powering Planet Earth - Energy Solutions for the Future, Wiley-VCH, 2013. KN06 | 8 ADVANCED ELECTRODE MATERIALS AND EVALUATION IN MICRO-FUEL CELLS PLATFORM Nicolas Alonso-Vante IC2MP UMR-CNRS 7285, Université de Poitiers, 4 rue Michel Brunet, F- 86022 Poitiers, cedex, France e-mail: [email protected] The development of advanced electrode materials for electrocatalysis is focused on the catalytic center and the supports to enhance the oxygen reduction reaction (ORR). Besides, the stability of any catalytic center is of paramount importance in low temperature fuel cell (FC) systems. In this sense, corrosion is a complex interplay, affecting not only the catalytic center but also the support, thus reducing at the end the performance, at the cathode side of the FC. Research on electrocatalysis [1-7], revealed that interaction between Pt nanoparticles (NPs) and supports lead to a change of the electronic properties of the catalytic center. Such an interaction between carbon, carbon-based and oxides with Pt nanoparticles can be electrochemically probed by examining the desorption energy of an adsorbed CO monolayer. All these aspects, to improve electrocatalyst materials, constitute indeed the core of electrochemical energy conversion devices, dominated by the optimization of kinetic activity, selectivity of catalysts and efficiency of whole cells, as well as on microfluidic systems. Membraneless microfluidic fuel cells, also called laminar fuel cells (LFFC) are promising power sources for powering portable devices [8]. However, we take advantage of this system as a platform to demonstrate the performance of the catalytic materials for the oxidation of various fuels to test the tolerance of the advanced electrode materials used as cathode in the way up to an integrated power source and micro-pump for Lab-on-Chip applications [9-10]. References [1] S. M. Unni, J. M. Mora-Hernandez, S. Kurungot, N. Alonso-Vante, ChemElectroChem 2015, 2 (9), 1339. [2] B. Ruiz Camacho, C. Morais, M. A. Valenzuela, N. Alonso-Vante, Catal. Today 2013, 202, 36. [3] N. Alonso-Vante, in Electrocatalysis in Fuel Cells, Vol. 9 (M. Shao, ed.), Springer London, 2013, p. 417. [4] L. Timperman, N. Alonso-Vante, Electrocatalysis 2011, 2, 181. [5] J. Ma, C. Canaff, N. Alonso-Vante, physica status solidi (a) 2013, 211, 2030. [6] J. Ma, A. Habrioux, C. Morais, A. Lewera, W. Vogel, Y. Verde-Gómez, G. RamosSanchez, P. B. Balbuena, N. Alonso-Vante, ACS Catalysis 2013, 3 1940. [7] N. Alonso-Vante, in Interfacial Phenomena in Electrocatalysis, Vol. 51 (C. G. Vayenas, ed.), Springer New York, 2011, p. 255. [8] S. Mousavi Shaegh, N. Nguyen, S. Chan, Int J Hydrogen Energy 2011, 35, 5675. [9] A.S. Gago, J.P. Esquivel, N. Sabaté, J. Santander, N. Alonso-Vante, Beilstein Journal of Nanotechnology 2015, 6, 2000. [10] A.S. Gago, Y. Gochi-Ponce, Y.-J. Feng, Esquivel, N. Sabaté, J. Santander, N. AlonsoVante, ChemSusChem 2012, 5, 1488. 9 | AL PHOTOPOLYMERS FOR STABLE SOLAR CELLS, SODIUM BATTERIES AND PHOTOELECTROCHROMIC WINDOWS Federico Bella,*,a Gianmarco Griffini,b George Leftheriotis,c Francesca Colò,b George Syrrokostas,c Jijeesh R. Nair,a Nikolaos Vlachopoulos,d Kazuteru Nonomura,d Shaik Mohammed Zakeeruddin,e Stefano Turri,b Michael Grätzel,e Anders Hagfeldt,d Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 - Torino, Italy. b Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 - Milano, Italy. c Energy and Environment Lab, Physics Department, University of Patras, 26504 - Panepistimioupoli Patron, Greece. d Laboratory for Photomolecular Science, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne (EPFL), Chemin des Alambics, Station 3, CH-1015 - Lausanne, Switzerland. e Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, School of Basic Sciences, Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 - Lausanne, Switzerland. e-mail: [email protected] The stability of energy devices is a critical (but often disregarded) issue, since great focus is often devoted to the efficiency records (even if these values rapidly decrease upon time). However, today's research in the energy field must be connected to concepts such as long-term stability, safety and environmental impact. In this work, we present free-radical photopolymerization as an attractive technique for the design and straightforward preparation of polymeric components for different energy devices (both storage and conversion). Photopolymerization represents a very attractive technique to this purpose, since it does not require solvents, catalysts, thermal treatments and purification steps. In the initial section, polymer electrolytes for dye-sensitized solar cells (DSSC) are demonstrated as alternatives to the standard liquid counterparts, using cobalt complexes as redox mediator. In addition, external luminescent and light-cured coatings are developed to further increase cell durability through a combined effect of UV-cutting, down-shifting and self-cleaning. In the second section, electrolytes and light-cured protective coatings are demonstrated for the first time in photoelectrochromic devices, thus leading to smart windows with highly stable characteristics and easy to be manufactured on a large scale. Finally, we show how Na-ion polymer batteries can be considered as an emerging, green and safe solution to the large storage of the electricity produced by solar panels. References [1] Bella, F.; Vlachopoulos, N.; Nonomura, K.; Zakeeruddin, S.M..; Grätzel, M.; Gerbaldi, C.; Hagfeldt, A. Chem. Commun. 2015, 51, 16308. [2] Bella, F.; Colò, F.; Nair, J. R..; Gerbaldi, C. ChemSusChem 2015, 8, 3668. [3] Bella, F.; Leftheriotis, G.; Griffini, G.; Syrrokostas, G.; Turri, S.; Grätzel, M.; Gerbaldi, C. Adv. Funct. Mater., DOI: 10.1002/adfm.201503762. O P 0 1 | 10 OPTIMIZATION OF AU NANOPARTICLES DECORATED BROOKITE TIO2 NANORODS FOR PHOTOELECTROCHEMICAL WATER OXIDATION: BULK VERSUS SURFACE PLASMONIC DECORATION Vladimiro Dal Santo,*,a Alberto Naldoni,a Francesco Malara,a Marcello Marelli,a Alessandro Beltram,b Tiziano Montini,b Ismael Romero-Ocaña,b Juan José Delgado Jaen,c Marta M. Mróz,d Tersilla Virgili,d Paolo Fornasiero.*,b a CNR – Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, 20133, Milano, Italy. Dipartimento di Scienze Chimiche e Farmaceutiche e Unita di Ricerca ICCOM-CNR, Università degli Studi di Trieste,Via L. Giorgieri 1, 34127 Trieste, Italy. c Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica,Facultad de Ciencias, Universidad de Cádiz, Campus Río San Pedro, 11510 Puerto Real, Cádiz,Spain d CNR - Istituto di Fotonica e Nanotecnologie (IFN) -, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo Da Vinci, 32 20133 Milano, Italy. b e-mail: [email protected], [email protected] Photoelectrochemical (PEC) water splitting represent one of the most promising technology for the direct conversion of solar energy to hydrogen in compact devices. Efficiency and scaling up of devices are still open issues. Semiconductor functionalization with plasmonic materials is one of the methods to improve performances, especially in thin film technologies. The location of the plasmonic component with respect to the semiconductor is one of the key design parameters for the development of efficient devices. While the geometry-dependent plasmonic enhancement was already investigated for solar cells [1], a similar study for PEC photoelectrodes is still lacking and works on embedded and surface plasmonic decoration have shown controversial results [2-4]. At the same time, the use of lessinvestigated brookite opens to significant improvement of the PEC performances. Here we report a study on the plasmonic geometry for PEC applications. Brookite TiO2 nanorods decorated with Au nanoparticles (NPs) were employed as building blocks for the development of photoelectrodes. Through a precise control of Au NPs deposition on brookite nanorods lateral facets, we clearly show that bulk versus surface plasmonic decoration generates dramatically different PEC activity. When Au NPs are homogeneously dispersed in the bulk of the film of brookite nanocrystals, photocurrent was depressed if compared to bare TiO2. Conversely, if Au NPs are preferentially deposited on the surface of the film near the electrode/water interface, a significant enhancement of photocurrent and four orders of magnitude longer charge carrier decay time were observed. Fig. 1 Photocurrent (J) curves for the brookite TiO2 (black curves), TiO2/Au-bulk (red References curves), and TiO /Au-surface (blue [1] Ferry, V. E.; Munday, J. N.; Atwater, H. A. Adv. Mater. 2010, 22 (43), 4794. [2] Zhan, Z.; An, J.; Zhang, H. ACS Appl. Mater. 2014, 6, 1139. [3] Thimsen, E.; Le Formal, F.; Grätzel, M.; Warren, S. C. Nano Lett. 2011, 11 (1), 35. [4] Thomann, I.; Pinaud, B. a; Chen, Z.; Jaramillo, T. F.; Clemens, B. M.; Mark, L. Nano Lett. 2011, 11, 3440. 11 | O P 0 2 ENERGY STORAGE AND CONVERSION SYSTEMS: FROM Li-ION TO Li-O2 BATTERIES Catia Arbizzani, Francesca Bigoni, Francesca De Giorgio, Irene Ruggeri, Francesca Soavi Alma Mater Studiorum Università di Bologna, Dipartimento di Chimica “Giacomo Ciamician”, via Selmi 2, 40126, Bologna (ITALY) e-mail: [email protected] The growing demand for energy with low or zero greenhouse-gas emission can be met only by renewable sources. The intermittent nature of most renewable sources requires electrical energy storage (EES) systems for an efficient use of generated energy. One of the most promising EES systems is the rechargeable battery, whose chemistry can be selected on the basis of the application [1]. Renewable energy storage and delivery according to the needs is fundamental for the interaction between EES and grids. U.S. Air Force has already proved the use of electric vehicle (EV) batteries to provide supplementary energy to the utility grid and a vehicle-to-home energy storage system has been field-tested by Nissan in Japan [2]. Li-ion batteries, with their great variety of chemistries, are the most advanced systems in terms of performance as testified by the increasingly widespread use in transport and in stationary applications. However, further improvements are needed: the energy density of current Li-ion technology is not sufficient for long driving range in EVs and the cost still limits the commercialization of large-size batteries. Hence, for next generation batteries, a renewed interest is focused on systems like Li-sulphur and Li-air batteries that could provide specific energy higher than Li-ion batteries [3]. In the present communication, strategies to improve high-voltage cathode performance for high-energy Li-ion battery [4] and a new design of Li-O2 battery that combines the high energy density of the Li-O2 battery with the flexible and scalable architecture of the redox flow batteries [5] will be presented and discussed. Acknowledgments. The authors wish to thank ENEA and Italy’s Ministero dello Sviluppo Economico for financial support under the Program “Ricerca di sistema elettrico, Materiali catodici per batterie litio ione a elevata energia” (2012-2014). Alma Mater Studiorum – Università di Bologna is also acknowledged for financial support (RFO, Ricerca Fondamentale Orientata) References [1] Dunn, B.; Kamath, H.; Tarascon, J.-M. Science 2011, 334, 928 [2] Raustad, R. A. The Electrochemical Society Interface 2015, 24, 53 [3] Bruce, P. G.; Freunberger, S. A.; L. Hardwick, J.; Tarascon, J.-M. Nature Materials 2012, 11, 19 [4] Arbizzani, C.; Da Col, L.; De Giorgio, F.; Mastragostino, M.; Soavi, F. J. Electrochem. Soc. 2015, 162, A2174 [5] Ruggeri, I.; Arbizzani, C.; Soavi, F. Energy Env. Sci., submitted O P 0 3 | 12 ELECTRODEPOSITION AND GALVANIC DISPLACEMENT: NEW ROUTES TO 3D CATALYSTS FOR CLEAN COMBUSTION AND H2 ELECTROLYTIC PRODUCTION S. Cimino,a G. Mancino,a M. Musiani,b L. Vázquez-Gómez,b E. Verlatob a b IRC - CNR, P.le V. Tecchio 80, 80125 Napoli, Italy IENI - CNR, C.so Stati Uniti 4, 35127 Padova, Italy e-mail: [email protected] The central role of electrochemistry in researches on renewable energy is well-known, but electrochemistry is commonly associated only to batteries, fuel cells and supercapacitors. However, electrodeposition and the closely-related spontaneous deposition processes may be advantageously exploited to prepare catalysts for partial and total low-temperature oxidation of various fuels and electrocatalysts for the electrolytic production of hydrogen. The (electro)catalysts whose preparation, characterization and testing is reviewed in the present communication consist of metal foams modified through the (electro)deposition of noble metal particles. Nickel and Fe-Cr-Al alloy foams are commercially available materials characterized by large surface area, efficient mass and heat transfer, and mechanical strength. Fe-Cr-Al alloys have also an outstanding resistance to hightemperature oxidation. The deposition of catalytic noble metals (e.g. Pt, Pd, Rh) may be achieved electrochemically or through spontaneous processes based on galvanic displacement reactions, occurring at open circuit, in which noble metal nuclei form on the foam surface, while the foam itself undergoes some dissolution, accompanied by surface roughening. In the materials prepared by either method, there is electrical contact between the foam support and the catalytic particles, in contrast to what happens in catalysts for gasphase oxidation reactions prepared by conventional approaches. Therefore, electrochemical methods, e.g. cyclic voltammetry, may be used for assessing the noble metal surface area, both in as-prepared samples and after their use in catalytic tests. Examples mentioned in the present communication include the low-temperature catalytic oxidation of CO and CH4 on Pd-modified Fe-Cr-Al alloy [1], the lowtemperature total combustion of methanol on Pt-modified Fe-Cr-Al foams [2], and the hydrogen evolution reaction on Pt-modified Ni foams [3]. Acknowledgements. The authors acknowledge the financial support of the Italian Ministry for Economic Development (MiSE-CNR Agreement on National Electrical System). References [1] S. Cimino, R. Gerbasi, L. Lisi, G. Mancino, M. Musiani, L. Vázquez-Gómez, E. Verlato, Chem. Eng. J. 2013, 230, 422-431. [2] S. Cimino, A. Gambirasi, L. Lisi, G. Mancino, M. Musiani, L. Vázquez-Gómez, E. Verlato, Chem. Eng. J. doi:10.1016/j.cej.2015.09.099 [3] S. Fiameni, I. Herraiz-Cardona, M. Musiani, V. Pérez-Herranz, L. Vázquez-Gómez, E. Verlato, Int. J. Hydrogen En. 2012, 37, 10507. 13 | O P 0 4 SURFACE REACTIVITY OF A CARBONACEOUS CATHODE IN Li-O2 CELLS Marco Carboni,a Sergio Brutti,b Andrea Giacomo Marrani*b a b Department of Chemistry, Sapienza University of Rome, Ple. Aldo Moro 5 00185, Rome, Italy. Department of Science, University of Basilicata, Viale Ateneo Lucano 10, 85100, Potenza, Italy. e-mail: [email protected], Li-O2 batteries are currently one of the most advanced and challenging electrochemical systems with the potential to largely overcome the performances of any existing technology for energy storage and conversion[1]. However, these optimistic expectations are frustrated by the still inadequate understanding of the fundaments of the electrochemical/chemical reactions occurring at the cathode side, as well as within the electrolyte and at the three-phase interface[2,3]. In this work, we studied the evolution of the morphology and composition of a carbonaceous cathode in the first discharge/charge in a Li-O2 cell with LiCF3SO3/TEGDME electrolyte by X-ray photoemission spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Experiments have been carried out ex situ on electrodes recuperated from electrochemical cells stopped at various stages of galvanostatic discharge and charge. Apparently, a reversible accumulation and decomposition of organic and inorganic precipitates occurs upon discharge and charge, respectively. These precipitations and decompositions are likely driven by electrochemical and chemical parasitic processes due to the reactivity of the cathode carbonaceous matrix. References [1] Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; M.; Tarascon, J-M. Nat. Mater., 2011, 11, 19-29. [2] McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.; Mori, T.; Scheffler, R.; Speidel, A.; Sherwood, M.; Luntz, A. C. J. Phys. Chem. Lett. 2012, 3 (20), 3043-3047. [3] Freunberger, S. A.; Chen, Y.; Drewett, N. E.; Hardwick, L. J.; Barde, F.; Bruce, P. G. Angew. Chem. Int. Ed. 2011, 50 (37), 8609-8613. O P 0 5 | 14 FAST ONE-POT SYNTHESIS OF MOS2/CRUMPLED GRAPHENE P−N NANONJUNCTIONS FOR ENHANCED PHOTOELECTROCHEMICAL HYDROGEN PRODUCTION Francesco Carraro, Laura Calvillo,* Mattia Cattelan, Stefano Agnoli, Gaetano Granozzia Department of Chemical Sciences, University of Padova, via Marzolo 1, Padua 35131, Italy e-mail: [email protected] Aerosol processing enables the preparation of hierarchical graphene nanocomposites[1,2] with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs, to hierarchical nanohybrids made up by nitrogen–doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), grazing incidence X-ray diffraction (GIXRD) and spectroscopic (high resolution photoemission, Raman and UV−visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation.[3] The activity of these materials is tested toward the photoelectrochemical production of hydrogen[4,5], obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p−n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation. References [1] Agnoli, S.; Granozzi, G. Surf. Sci. 2013, 609, 1. [2] Mao, S.; Wen, Z.; Kim, H.; Lu, G.; Hurley, P.; Chen, J. ACS Nano 2012, 6, 7505. [3] Benck, J.D.; Hellstern, T.R.; Kibsgaard, J.; Chakthranont, P.; Jaramillo, T. ACS Catal. 2014, 4, 3957. [4] Meng, F.; Li, J.; Cushing, S. K.; Zhi, M.; Wu, N. J. Am. Chem. Soc. 2013, 135, 10286. [5] Li, Y.; Wang, H.; Xie, L.; Liang, Y.; Hong, G.; Dai, H. J. Am. Chem. Soc. 2011, 133, 7296. 15 | O P 0 6 ELECTRO-SPUN CARBON-ENRICHED COBALTOSIC OXIDE FIBROUS MATS AS BINDER-FREE ELECTRODE MATERIALS IN FLEXIBLE Li-ION BATTERIES Saveria Santangelo,*,a Patrizia Frontera,a Nicola Pinna,b Yafei Fan,b Fabiola Pantò,c Sara Stelitano,d Pierluigi Antonuccia a Dipartimento di Ingegneria Civile, dell’Energia, dell’Ambiente e dei Materiali (DICEAM), Università “Mediterranea”, 89122 Reggio Calabria, Italy b Humboldt Universität zu Berlin, Institut für Chemie, 12489 Berlin, Germany c Dipartimento di Ingegneria dell’Informazione, delle Infrastrutture e dell’Energia Sostenibile (DIIES), Università “Mediterranea”, 89122 Reggio Calabria, Italy d Dipartimento di Fisica (DF), Università della Calabria, 87036 Arcavacata di Rende, Italy e-mail: [email protected] Lightweight, large capacity, high rate capability and cyclic stability are the basic requirements for lithium-ion batteries (LIBs), currently representing the dominant power source for portable electronic devices. Flexibility is further needed to meet the increasing demand for devices with shape versatility. Low electronic conductivity and poor transport properties of common electrode materials have encouraged the use of carbon additives, such as nanotubes (N) and graphene (G) [1]. Thanks to its simplicity, cheapness, versatility and scalability electro-spinning (ES) is a very commercially competitive technique for the synthesis of high-surface area fibrous mats [2]. This work shows that flexible C-enriched cobaltosic oxide (Co3O4) fibrous mats to be used as binder-free electrode materials in LIBs can be prepared by ES. Polyacrylonitrile, N,N-dimethylformamide and Co acetate are utilised as polymer, solvent and oxide precursor, respectively; N and G are evaluated as carbonaceous additives. Pure Co3O4 powders or flexible C/Co3O4, C/N/Co3O4 and C/G/Co3O4 fibrous mats (Figs. 1a−b) can be obtained by proper thermal treatments of the as-spun fibres and additive insertion in the spinnable solution. Thermal treatment does not influence the oxide stoichiometry (Fig. 1c); G is dispersed within the fibrous mat more uniformly than N. Anode consisting of pure Co3O4 powders (with binder) exhibits higher initial capacity but very scarce stability (Fig. 1d); conversely, in spite of the lower initial capacity, binder-free anode realised with C/G/Co3O4 fibrous mat appears to be by far more stable. Fig. 1. (a) SEM and (b) digital images of flexible C/G/Co3O4 fibrous mats. (c) Raman spectra of the samples and (d) results of half-cell tests (current density: 100 mA/g). References [1] Toprakci, O.; Toprakci, H.A.K.; Ji, L.; Xu, G. et al. X. ACS Appl. Mater. Interf. 2012, 4, 1273. [2] Frontera, P.; Malara, A.; Stelitano, S.; Fazio, E. et al. Mater. Chem. Phys. 2015, 153, 338. O P 0 7 | 16 STRUCTURE AND CATALYTIC MECHANISMS IN WATERSPLITTING AMORPHOUS OXIDES Leonardo Guidoni a Università degli Studi dell’Aquila, Dipartimento di Scienze Fisiche e Chimiche, L’Aquila, Italy e-mail: [email protected] Several synthetic catalysts, containing different transition-matal-oxo cores have been recently proposed, but earth-abundant Fe, Ni, Mn, Co amorphous oxides likely represent the most promising route towards technologically relevant and low cost photo-electrolytic cells. [1] A thorough understanding of water oxidation promoted by these amorphous transition-metal oxides requires detailed insight in the atomistic texture and in the electronic properties of the catalysts. In combination with x-ray absorption spectroscopy measurements, computer simulations can provide important atomic-level structural information that may help to design structural models of the catalysts. In the present contribution we will use quantum chemistry and first principles molecular dynamics to investigate the structural and catalytic properties of cluster models of different water splitting catalysts. For the cobalt-based catalyst (CoCat) in explicit water solution, we have provided insights into the pathways for oxygen evolution by identifying the formation of Co(IV)-oxyl species as the driving ingredient for the activation of the catalytic mechanism. [2] For the manganese-based catalyst, in collaboration with H. Dau and I. Zaharieva (Freie Univ. Berlin), we have carried out accurate DFT simulations, comparing the obtained results with the XAFS measurement collected, thus revealing the details of the structural motifs of the catalytic sites. [3] Comparison between these results and those obtained for the catalytic core of the natural water-splitting enzyme (Photosystem II) [4] suggests differences and similarities between the inorganic and the biological catalysts. Fig.1 – Low barrier hydrogen bond at the interface between the Cobalt Catalyst and water Fig.2 – Structural motifs proposed by an integrated XAFS / electronic structure approach applied to the Manganese Catalyst for water-splitting References [1] Kanan, M.W. et al., Science 2008, 321, 1072. Nocera, D. Acc.Chem.Res. 2012, 45, 767. Risch, M. et al. Chem. Comm. 2011, 47, 11912. Bergmann, A. et al. En. & Env. Sci. 2013, 6, 2745. Suntivich, J. et al. Science 2011, 334 1383. [2] Mattioli, G.; Giannozzi, P.; Amore Bonapasta, A.; Guidoni, L.; J.A.C.S. 2013, 135, 15353. [3] Mattioli, G.; Zaharieva, I.; Dau, H; Guidoni, L.; J.A.C.S. 2015, 137, 10254. [4] Bovi, D.; Narzi, D.; Guidoni, L. Ang.Chemie 2013, 125, 11960. Narzi, D.; Bovi, D.; Guidoni, L. P.N.A.S. 2014, 111, 8723. 17 | O P 0 8 Co3O4 ANODE MATERIAL FOR Na-ION RECHARGEABLE BATTERIES Riccardo Ruffo,a* Gianluca Longoni,a Claudio M. Mari,c a Università di Milano Bicocca, via Cozzi 55, Milano, Italy e-mail: [email protected] Lithium ion batteries play a predominant role in the market of power sources for cordless devices with a production higher than 100 million cells/month and about 1500 ton/month of electrode materials. These figures may increase in the future due to the use of such batteries in automotive application which implies the increasing of lithium raw material (Li2CO3) consumption. Nowadays, the availability of Li2CO3 is restricted to few countries and lithium may become a strategic material in the near future with the booming of its cost and the raising of geopolitical issues. For this reasons Na-ion batteries are getting increasing attention thanks to the higher availability of Na sources and the possibility to drive down the energetic demand connected to raw materials extraction and processing. However, the development of the sodium ion based battery technology requires the discovery and the investigation of new electrode materials with reversible Na+ intercalation reaction. Aim of the present contribution is to describe the preparation and the characterization of a series of Co3O4 specimens with different morphologies. The Co3O4 compound has been taken into account considering the high theoretical specific capacity (890 mAh·g1 ) and the possibility to use soft chemistry route (hydrothermal synthesis). In particular, three different morphologies have been considered, obtained varying the preparation conditions. The powders show hierarchical structures made by nanocrystallites organized in secondary morphologies; NR7, NR 16, and NR 21 samples, indeed, are made by platelet, needle, and agglomerate particles, respectively. The best performances are delivered by NR 16, with a reversible capacity of about 500 mAh/g at 0.1C for 50 cycles in the potential range 1.0/0.0 V vs. Na+/Na. The materials suffers of low first cycle efficiency, an issue which has been tackled by using a preliminary sodiation step. Figure 1. Electrochemical performances of the three Co3O4 morphologies. O P 0 9 | 18 BaCe0.85-XZrXY0.15O3-δδ AND Y- OR Gd-DOPED CeO2 CERAMICCERAMIC COMPOSITE MEMBRANES FOR HYDROGEN SEPARATION Elena Rebollo,* a Cecilia Mortalò,a Sonia Escolástico,b Stefano Boldrini,a Simona Barison,a S. Escorihuela,b José María Serra,b Monica Fabrizioa a Istituto per l’Energetica e le Interfasi, CNR-IENI, Corso Stati Uniti 4, 35127, Padova (Italy). Instituto de Tecnología Química, Universidad Politécnica de Valencia – Consejo Superior de Investigaciones Científicas, Av. De los Naranjos s/n. 46022 Valencia (Spain). b e-mail: [email protected] The efficient separation of pure H2 from a gas mixture is a critical stage for large scale production of this energy carrier. H2-selective membranes represent an appealing option to recover hydrogen from low-quality gas e.g. from biomass. Protonic-ceramic have received considerable attention due to their potential application as mixed ionicelectronic conductor (MIEC) separation membranes for H2 production. In MIEC membranes, the separation and transport of H2 occurs electrochemically in the form of protons and electrons. In a non-galvanic mode, the membrane must have both high electronic and high proton conductivities [1]. Still, a stable single phase material with those properties is rather challenging. Indeed, an enhancement of proton conductivity through doping is generally related to a decrease on the electronic conductivity and on the stability of this kind of ceramics. Another strategy is to obtain the desired functional properties through composite membranes formed by two compatible ceramic phases. In this work, BaCe0.85-xZrxY0.15O3-δ perovskites and doped CeO2 fluorites have been combined in different volume ratios to fabricate “ceramic-ceramic” composite membranes for H2 separation. It has been demonstrated that barium cerate-zirconate solid solutions BaCe0.85-xZrxY0.15O3-δ (x: 0.20, 0.30) stabilize the perovskite structure without sacrificing protonic conductivity [2]. On the other hand, doped ceria oxides shows remarkable n-type electronic conductivity under H2 separation conditions. Furthermore, they enhance the stability against CO2 and H2O of the cerate material in the composite membranes. The optimal preparation and sintering conditions of the dense membranes have been determined through XRD and SEM techniques. OCV and a.c. impedance spectroscopy (EIS) have been carried out to study the electrochemical behaviour of the composites. In addition, the stability against CO2 and syn-gas (mandatory under operational H2 separation conditions) was evaluated by different methods. Finally, the H2-permeation of these dense membranes was measured, reaching hydrogen fluxes among the highest achieved for bulk mixed protonic-electronic membranes reported so far. References [1] T. Norby, R. Hausgrud, Nonporous Inorganic Membranes, 2006, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. [2] S. Barison Et al., J. Mater. Chem., 2010, 18, 5120- 5128. 19 | O P 1 0 NOVEL LIQUID AND POLYMER ELECTROLYTES FOR LITHIUM-SULFUR BATTERIES Fabiana Savi,a Lucia Lombardo,a Luis Aguilera,b Khalid Elamin,b Maria Assunta Navarra,a Aleksandar Matic,b Stefania Paneroa a Department of Chemistry, Sapienza University of Rome, Piazzale Aldo Moro 5, 00185 Rome, Italy Department of Applied Physics, Chalmers University of Technology, Origovägen 6b, 41296 Göteborg, Sweden. b e-mail: [email protected], A major hurdle still hindering the practical development of the highly desirable lithium-sulfur batteries is the solubility in organic, carbonate-based electrolytes of polysulfide compounds formed as intermediates during charge and discharge processes. This high solubility results in a loss of active mass, which is reflected in a low utilization of the sulfur cathode and in severe capacity decay upon cycling. The dissolved polysulfide anions, by migration through the electrolyte, may react with the lithium metal anode to form insoluble products on its surface; this process also negatively impacts the battery operation. Various strategies to address the solubility issue have been explored, including the design of modified organic liquid electrolytes, the use of ionic liquid solutions and of polymer electrolytes [1, 2]. In this work we present a combined strategy, where optimized liquid electrolytes, composed by ether-based solvents and an ionic liquid additive, were used to swell a selected polymer matrix. This allows the formation of composite, highly conductive, gelled polymer electrolytes able to control the dissolution of the sulfide anions. In our approach, a dry poly(ethylene oxide) (PEO) membrane was first prepared, through a solvent-free route [3, 4], and then activated by the liquid electrolyte, according to a well addressed swelling procedure. Thermal, spectroscopical and electrochemical characterizations were performed on both liquid and gelled polymer electrolytes and will be discussed. The successful practical application in Li-S cells was demonstrated by prolonged galvanostatic cycles where very high and stable capacity values (i.e., 900 mAh/g) were achieved. Acknowledgments. The results of this work have been obtained by the financial support of the European Community within the Seventh Framework Program LISSEN (Lithium Sulfur Superbattery Exploiting Nanotechnology) Project (project number 314282). References [1] Junghoon Kim , Dong-Ju Lee , Hun-Gi Jung , Yang-Kook Sun , Jusef Hassoun , Bruno Scrosati, Adv. Funct. Mater. 2013, 23, 1076 [2] Rezan Demir-Cakan, Mathieu Morcrette, Gangulibabu, Aur´elie Gu´eguen, R´emi Dedryv`ere, Jean-Marie Tarascon, Energy Environ. Sci. 2013, 6, 176 [3] P.P Prosini, S Passerini, R Vellone, W.H Smyrl - J. Power Sources 1998, 75, 73 [4] G.B Appetecchi, S Scaccia, S Passerini - J. Electrochem. Soc. 2000, 147, 4448 O P 1 1 | 20 [NiFe]-HYDROGENASES: A DFT INVESTIGATION OF THE INACTIVATION MECHANISMS UNDER AEROBIC AND ANAEROBIC CONDITIONS Breglia R.,a Greco C.,a De Gioia L.,b Bruschi M.a a Department of Earth and Environmental Sciences, University of Milano-Bicocca, Piazza della Scienza 1 20126-Milan (Italy). b Department of Biotechnology and Biosciences, University of Milano-Bicocca, Piazza della Scienza 2 20126-Milan (Italy) email:[email protected] [NiFe]-hydrogenases are a class of metallo-enzymes that catalyse the reversible interconversion of protons and reducing equivalents into molecular hydrogen. These enzymes have become a field of intensive research in recent years due to a continuously increasing interest into attaining hydrogen-based energy sources. Indeed, the high catalytic efficiency and the absence of expensive metals in their active site, makes the [NiFe]-hydrogenases a very promising target for reverse engineering studies aimed at the development of bioinspired catalysts. The active site of these enzymes is composed by a bimetallic cluster of iron and nickel atoms bridged by two cysteine residues. Two further cysteine residues are terminally bounded to the Ni atom while two CN and one CO ligands coordinate the Fe atom. [NiFe]-hydrogenases can be inactivated under both aerobic and oxidizing anaerobic conditions yielding two distinct forms labelled Ni-A and Ni-B, which differ in the time required for the reactivation under reducing conditions; few minutes for Ni-B and several hours for Ni-A. The Ni-A/Ni-B ratio is strongly influenced by the type of oxidant, as well as the initial overall redox state of the enzyme. Several X-ray crystallographic structures of oxidized [NiFe]-hydrogenases have been assigned to the Ni-B and Ni-A states. However, while there is a general consensus on the Ni-B state as containing an hydroxide ligand bridging NiIII and FeII atoms, the nature of Ni-A is still controversial. Prompted by the above observation we have carried out quantum mechanics calculations in the framework of the Density Functional Theory (DFT) on a very large model of the active site in order to characterize the nature of the Ni-A state, and to disclosure the inactivation mechanisms under aerobic and anaerobic conditions. The results of these calculations support the recent X-ray assignment of the Ni-A state as containing a hydroxide ligand bridging the two metallic ions and a bridging cysteine oxidized to its sulfanated form. In addition, plausible reaction pathways leading the inactive states of the enzyme have also been proposed, enabling to identify the conditions required for the selective oxidation to Ni-B and Ni-A forms. The presented results may be exploited in biotechnological applications of [NiFe]-hydrogenases and in the design of related bioinspired synthetic catalysts. References [1] W. Lubitz, H. Ogata, O. Rüdiger, E. Reijerse Chem. Rev., 2014, 114, 4081-4148. [2] M. Bruschi, M. Tiberti, A. Guerra, L. De Gioia J. Am. Chem. Soc. 2014, 136, 1803-1814. [3] Volbeda, • L. Martin, • E. Barbier,• O. Gutierrez-Sanz, • A. L. De Lacey ,• P.-P. Liebgott ,• S. Dementin, • M. Rousset, JC. Fontecilla-Camps J. Biol. Inorg. Chem. 2015, 20, 11-22. 21 | O P 1 2 RATIONAL DESIGN OF TRIPLE CONDUCTING OXIDES FROM MIXED ION-ELECTRON CONDUCTORS: AB INITIO STUDY OF A-DOPED Sr2Fe1.5Mo0.5O6-δ Ana Belén Muñoz-García,*,a Michele Pavonea a Department of Chemical Sciences, Univeristy of Naples Federico II, Comp. Univ. Monte S. Angelo, Via Cintia 26, 80126, Naples, Italy. e-mail: [email protected] Electrolyzer and fuel cells based on proton-conducting oxides (PC-SOEC/FCs) are gaining grounds in the energy conversion scenario thanks to the high proton conductivity of protons at intermediate temperatures.1,2 Major advances on PCelectrolytes (e.g., BaCeO3 and LaNbO4 derivatives)3 have not been sufficient to bring PC-SOEC/FCs to an applicative stage because of severe limitations at electrodes, which must comply several crucial requirements: high catalytic activity, high electron and proton conductivity. Current electrodes are mostly composites, made of mixed (oxide) ion-electron conductor (MIEC) oxides and the PC-electrolyte. Only recently, triple (e-/O2-/H+) conducting oxides (TCOs), i.e. MIEC with enhanced proton transport capability, have been proposed as single-phase electrodes instead of composites.4 In this work, we evaluated the TCO properties of a double perovskite Sr2Fe1.5Mo0.5O6-δ (SFMO) with state-of-the-art DFT+U calculations. SFMO has been proposed as anode and cathode material for symmetric oxide-conducting SOFCs because it ensures good catalytic activity, excellent MIEC properties and remarkable stability in both oxidizing and reducing environment.5 SFMO is inherently non-stoichiometric,6 which turns this MIEC into a good candidate for proton conduction provided that oxygen vacancies allow the incorporation of protons via water dissociative uptake into the lattice. Thus, we analyzed hydration properties and proton migration barrier heights in SFMO and in two derivatives, namely Sr0.875Ba0.125Fe1.5Mo0.5O6-δ and Sr0.875K0.125Fe1.5Mo0.5O6-δ. Ba and K substitutions at the A-site of SFMO perovskite affect both the structural and electronic features, boosting the proton transport of SFMO. In particular, aliovalent K doping results in a higher concentration of oxygen vacancies and in a lower migration barrier. From analysis of our ab initio results, we identified key structural parameters that promote the proton transport between oxygen sites and we designed new promising TCO candidates for PC-SOEC/FC electrodes. References [1] Bi, L.; Boulfrad, S.; Traversa, E. Chem. Soc. Rev. 2014, 43, 8255. [2] Fabbri, E.; Pergolesi, D.; Traversa, E. Chem. Soc. Rev. 2010, 39, 4355. [3] Malavasi, L.; Fisher, C. A.; Islam, M. S. Chem. Soc. Rev. 2010, 39, 4370. [4] Kim, J.; Sengodan, S.; Kwon, G.; Ding, D.; Shin, J.; Liu, M.; Kim, G. ChemSusChem 2014, 7, 2811. [5] Liu, Q.; Dong, X.; Xiao, G.; Zhao, F.; Chen, F. Adv. Mater 2010, 22, 5478. [6] Muñoz-García, A. B.; Bugaris, D. E.; Pavone, M.; Hodges, J. P.; Huq, A.; Chen, F.; zur Loye, H. C.; Carter, E. A. J. Am. Chem. Soc. 2012, 134, 6826. O P 1 3 | 22 THIOPHENE-BASED PHENOTHIAZINES FOR DYE-SENSITIZED SOLAR CELLS AND PHOTOCATALYTIC H2 PRODUCTION Bianca Cecconi,a Norberto Manfredi,a Riccardo Ruffo,a Tiziano Montini,b Ismael Romero-Ocaña,b Paolo Fornasiero*,b Alessandro Abbotto*,a a Department of Materials Science and Solar Energy Research Center MIB-SOLAR, University of Milano-Bicocca, and INSTM Milano-Bicocca Research Unit, Milano, Italy b Department of Chemical and Pharmaceutical Sciences, University of Trieste, ICCOM-CNR Trieste Research Unit, and INSTM Trieste Research Unit, Trieste, Italy. e-mail: [email protected] Dye-sensitized photocatalytic hydrogen production (Fig. 1) via organic metal-free sensitizers has been so far scantly investigated in favor of organometallic systems. Indeed, metal-free sensitizers offer a number of advantages over organometallic counterparts such as larger structural variety, deeper control of molecular, optical and energetic properties, ease of synthesis and purification, and lower manufacturing costs. In the frame of our investigation on dye-sensitized solar cells (DSSC) and anchoring to TiO2 in the last years we have pioneered a multi-branched multi-anchoring D(-π-A)2 geometry, now widely used in the DSSC field.1-3 The multibranched molecular architecture demonstrated enhanced optical and light harvesting ability, stronger anchoring to TiO2 surface and photoelectron injection to the semiconductor conduction band, and improved long-term stability. In this work we present the application of specifically engineered dibranched dyes to the dye-sensitized photocatalytic hydrogen production. Namely, we tested a series of D-(π-A)2 dyes where D is a phenothiazine donor core, A is the acceptor-anchoring cyano-acrylic group, and π varies as different thiophene derivatives (Figure 2).4 Design of the π-spacer afforded significant enhancement of optical properties, in terms of redshifted absorption and up to a four-fold molar absorptivity. Compared to the reference dye with no π-spacer,5 the new sensitizers revealed improved stability after longer irradiation times and enhanced performances after an initial activation period. Fig. 1 – Dye-sensitized H2 production mechanism. Fig. 2 –Sensitizers developed in this work. References [1] Abbotto, A.; Manfredi, N.; Marinzi, C.; De Angelis, F.; Mosconi, E.; Yum, J. H.; Zhang, X. X.; Nazeeruddin, M. K.; Gratzel, M. Energy Environ. Sci. 2009, 2, 1094. [2] Abbotto, A.; Leandri, V.; Manfredi, N.; De Angelis, F.; Pastore, M.; Yum, J. H.; Nazeeruddin, M. K.; Gratzel, M. Eur. J. Org. Chem. 2011, 6195. [3] Manfredi, N.; Cecconi, B.; Abbotto, A. Eur. J. Org. Chem. 2014, 7069. [4] Cecconi, B.; Manfredi, N.; Ruffo, R.; Montini, T.; Romero-Ocaña, I.; Fornasiero, P.; Abbotto, A. ChemSusChem 2015, n/a. [5] Lee, J.; Kwak, J.; Ko, K. C.; Park, J. H.; Ko, J. H.; Park, N.; Kim, E.; Ryu, D. H.; Ahn, T. K.; Lee, J. Y.; Son, S. U. Chem. Comm. 2012, 48, 11431. 23 | O P 1 4 NANOSTRUCTURED OXYGEN SELECTIVE MEMBRANE FOR Li-AIR BATTERY OPERATING IN AMBIENT AIR Julia Amici, a Mojtaba Alidoost, a Juqin Zeng, a Carlotta Francia, a Silvia Bodoardo, Nerino Penazzi a a a Department of Applied Science and Technology (DISAT), Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino, Italy. e-mail: [email protected], The demand for high-energy storage systems is constantly increasing, as is the interest to explore alternatives to commercially available batteries. The rechargeable Li-air battery represents an exciting opportunity to design batteries that may satisfy some of the requirements of our future by coupling the light Li metal with the inexhaustible source of O2 of the surrounding air, resulting in high theoretical specific energy density [1, 2, 3]. Currently, most of the researches on the Li-air battery comprise a cell fed with pure O2 allowing that way to maintain long-term operation, owing to the high O2 concentration free of contaminants. However, for many practical applications such as EV, air is the only viable option to supply the battery. In this context, moisture and gases other than O2 may cause side reactions and corrosion. Herein, we report a facile strategy to fabricate an effective oxygen selective membrane with poly(vinylidene fluoride co-hexafluoropropylene) (PVDF-HFP) via non-solvent induced phase separation, casted as a 240 micron thin sheets for cell protection in ambient air condition. The use of different additives helps enhancing the barrier properties as well as the membrane specificity toward O2. For instance, sacrificial silica nanoparticles (SiO2 NPs) were incorporated into the precursor solution to create a controlled alveolar-like structure inside the membrane and then load it with polydimethylsiloxane (PDMS) under vacuum. By entrapping silicone oil within the porous structure of the polymer, the Li-air cell was able to discharge in ambient air for long period operation. Galvanostatic charge-discharge tests in a potential/time controlled mode confirmed the ability of the cell with the membrane to reach, in ambient air, nearly the same performances that a dry oxygen fed cell, as demonstrated on Fig. 1. PURE O2 FLOW 3ml/min no membrane Dry-room AIR , 17%RH SiOil/PVDF SiOil/PVDF membrane Figure 1: Cycling test of a cell without membrane fed with O2 flow (left) and a cell with membrane in air (17% RH) (right). References [1] Mulder, M.; Basic principles of membrane technology, , Kluwer Academic Publishers 1996, 2nd edn., London. [2] Kurumada, K.; Kitamura, T.; Fukumoto, N.; Oshima, M.; Tanigaki, M.; Kanazawa, S. J. Membr. Sci. 1998, 149, 51. [3] Zhang, J.; Xu, W.; Li, X.; Liu, W. Journal of the Electrochemical Society. 2010, 157, A940. O P 1 5 | 24 A TERNARY ZnAlIr LAYERED HYDROXIDE AS EFFICIENT WATER OXIDATION HETEROGENEOUS CATALYST Lucia Fagiolari,a Ferdinando Costantino,a Riccardo Vivani,b Alceo Macchioni*,a a Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, via Elce di Sotto, 8, 06123 – Perugia (Italy) b Dipartimento di Scienze Farmaceutiche, Università degli Studi di Perugia, via del Liceo, 1, 06123 – Perugia (Italy) e-mail: [email protected] Water oxidation is considered the bottleneck for the development of an artificial photosynthetic apparatus aimed at the green production of renewable fuels1. Many materials2 and molecules3 have been reported as catalysts for water oxidation. Nevertheless, the performances are still unsatisfactory. Herein, we report a ternary Layered Hydroxide, of chemical formula [Zn0.667Al0.306Ir0.027(OH)2]Cl0.333•0.4H2O as a remarkably efficient and robust water oxidation catalyst. ZnAlIr Layered Hydroxide has been obtained by the replacement of some Al(III) with Ir(III) ions in a ZnAl Layered Double Hydroxide (LDH) structure. LDHs are a class of anionic clays, based on brucite (Mg(OH)2)-like layers, in which some divalent cations are substituted by trivalent ions, affording positively-charged sheets. The charge is balanced by the intercalation of anions in the interlayered region4. The layered material was synthesized by the urea hydrolysis method, starting from the chloride salt of the three metal cations. The X-ray pattern shows good cristallinity and the typical reflections of ZnAl LDH in the chloride form, suggesting that the brucite structure is maintained. EDX and TEM images show that iridium is uniformly distributed throughout the particles. The performance of ZnAlIr LDH toward water oxidation was evaluated using NaIO4 as sacrificial oxidant. The kinetics were followed by measuring the evolved oxygen in the gas phase through differential manometry. The material shows excellent stability and recyclability in water, since the catalytic activity is the same after eight consecutive runs on the same solid. The mean TOF is 2 and 20min-1 in unbuffered solution and in phosphate buffered solution at pH 7.7, respectively. The highest measured TOF and TON are 100min-1 and 15000, respectively. The X-ray spectrum of the solid after the catalysis is the same than before, therefore no significant structural modification happens during catalysis. All seems to indicate that these Layered Hydroxides are promising materials to be used as water oxidation heterogeneous catalysts. References [1] Balzani, V.; Credi, A.; Venturi, M.; ChemSusChem, 2008, 1, 26-58 [2] Kudo, A.; Miseki, Y.; Chem. Soc. Rev., 2009, 38, 253-278 [3]Blakemore, J:D.; Crabtree, R.H.; Brudvig, G.W.; Chem. Rev., 10,1021/acs.chemrev.5b00122 [4] Alberti, G.; Bein, T.; Elsevier Science Ltd Press, 1996, Chap. 8, Vol. 7 2015, DOI: 25 | O P 1 6 SUISTAINABLE SYNTHESIS OF PYRITE NANOPARTICLES FOR SOLAR ENERGY CONVERSION AND STORAGE Andrea Giaccherinia, Ivan Colantonib, Francesco D'Acapitoc, Giordano Montegrossid, Antonio De Lucaa, Maurizio Romanellia, Francesco Di Benedettoe , Massimo Innocentia a Chemistry Department, University of Firenze, Firenze, Italy. Department of Physics, Sapienza University of Rome, Rome, Italy. c CNR‐IOM‐OGG c/o ESRF, Grenoble, France. d The Institute of Geosciences and Earth Resources, CNR, Firenze, Italy. e Department of Earth Sciences, University of Firenze, Firenze, Italy. b e-mail: [email protected] Interest for mineral nanoparticles has emerged during last decade, chalcogenides containing elements such as Cu, Sn, Fe and Zn, constitute a class of compound characterized by low-cost of starting materials and low-environmental impact. This study focus on FeS2, pyrite, nanoparticles considered useful for both solar energy conversion and storage (in the Li ion batteries), namely taking into account the persistence of the main properties of the bulk FeS2. Moreover, the presence of a defect structure near to the particle surface could be potentially applied to specific reactive processes (as e.g. in waste remediation). Pyrite nanoparticles were obtained through a one-pot solvothermal synthesis, carried out at room pressure and mild temperature (≈180 °C); in the reaction environment the co-generation of the sulfide anion is operated. This approach, limits the environmental concerns, avoiding the involvement of solvents, surfactants, capping agents, ligand molecules in the process. Characterization of the obtained products was thus performed, including SEM micromorphology, XRD, Diffuse Reflectance Spectroscopy, and XAS spectroscopy (both in the XANES and EXAFS regions). From a morphological point of view, the products reveal the presence of aggregates of individual particles having an approximate dimension of few hundreds of nm. The lack of a definite crystal morphology is attributed to the absence in the batch of reactants of specific surfactants. Nevertheless, particles exhibit an euhedral morphology. The XRD and, qualitatively, XANES patterns point to pyrite as the unique product of the synthesis. The Scherrer analysis of the profile parameters suggest that the individual particles observed by SEM inspection are clusters of smaller particles, having a mean size of ~25 nm. Moreover, SEM-EDX analysis performed on the sample reveald a 1at% of Chloride in the sample. XRD measurements point to a significant increase of the Fe-S bond distance (+1.7%), this change is attributed to the presence of Chloride ions in the crystal structure of Pyrite NPs. The DRS spectra, elaborated through the use of the Tauc plot, confirm that the pyrite nanoparticles exhibit an optical behavior indistinguishable from that of the bulk pyrite. The results of the present study point to the one pot synthesis of pyrite nanoparticles as an efficient and “green” way which constitute a promising process for the industrial scale up . O P 1 7 | 26 Co-AXIAL NANOSTRUCTURES FOR ENERGY CONVERSION: SYNERGIC EFFECTS BETWEEN CARBON NANOTUBES AND METAL OXIDES Giovanni Valenti,a Alessandro Boni,a Matteo Cargnello,b Massimo Marcaccio,a Stefania Rapino,a Marcella Bonchio,c Maurizio Prato,b Paolo Fornasiero,b Francesco Paoluccia a) Department of Chemistry “G. Ciamician” University of Bologna, via Selmi 2, 40126 Bologna, Italy Department of Chemical and Pharmaceutical Sciences, Center of Excellence for Nanostructured Materials (CENMAT), University of Trieste, Italy c) Department of Chemical Sciences and ITM-CNR, University of Padova, via F. Marzolo 1, 35131 Padova, Italy b) e-mail: [email protected] The growing need for energy on global scale and the realization that the so called oilbased economy cannot sustain our world anymore, prompted researchers to find new ways to “power” the planet.1 In particular a lot of efforts have been done in the field of chemical energy conversion, that remains very challenging because of the requirement for higher efficiencies.2 The splitting of water to high energy chemical fuels is one of the most attractive and pursued alternatives; among the major issues there is the need to find catalytic systems that are able to boost the overall reaction efficiently and durably.3 In this context our group recently focused the attention on the study of catalytic systems for the oxygen evolution reaction (OER).4 Our last efforts have been done in the development of new C-based nanocomposites that combine the unique properties of multiwall carbon nanotubes (MWCNTs), metal oxides (TiO2 and CeO2) and Pd nanocomposites MWNT@Pd/TiO2 and nanoparticles (Pd NPs).5 The MWNT@Pd/CeO2 have been designed and evaluated as electrocatalyst for the reaction of hydrogen evolution (HER) and for the CO2 reduction, respectively. Both systems exhibit very good performances and efficiencies, showing physical and chemical properties that differ to those expected from the simple sum of the individual building blocks. Due to these synergic effects, we shed light on the role of the MWCNTs in terms of their influence on the electronic properties of the two semiconductors (e.g. presence of surface states and different doping levels), resulting in better electrocatalytic activities. References [1] Armaroli, N.; Balzani, V. Angew. Chem. Int. Ed., 2007, 46, 52-66. [2] Centi, G. and S. Perathoner, ChemSusChem, 2010, 3, 195-208. [3] Subbaraman, R.; Tripkovic, D.; Strmcnik, D.; Chang, K-C.; Uchimura, M.; Paulikas, A. P.; Stamenkovic, V.; Markovic, N. M. Science, 2011, 334, 1256-1260. [4] Toma, F.; Sartorel, A.; Iurlo M. et al., Nature Chemistry, 2010, 2, 826-831. [5] a) Cargnello M. et al. J. Am. Chem. Soc., 2012, 134, 11760-11766. b) Mazzaro, R.; Boni, A.; Valenti G.; et al. 2015, 4, 268-273. c) Valenti, G.; Boni, A.; Cargnello, M.; et al. submitted 27 | O P 1 8 QUANTUM CHEMICAL CALCULATION OF ENERGY TRANSFER AND PHOTOINDUCED ELECTRON TRANSFER RATES IN DONOR-BRIDGE-ACCEPTOR SYSTEMS Lorenzo Cupellini, Stefano Caprasecca, Benedetta Mennucci Dipartimento di Chimica e Chimica Industriale, Via Moruzzi 13, 56124, Pisa, Italy. e-mail: [email protected] Excitation energy transfer (EET) and photoinduced electron transfer (ET) have a fundamental importance in natural and artificial light harvesting. Both ET and EET have been extensively studied in molecular dyads and Donor-Bridge-Acceptor (D-B-A) systems. [1] The energy and electron transfer properties of these assemblies can be tuned by appropriately changing substituents on D and A and the nature of the bridge. A detailed theoretical analysis of the mechanisms of ET and EET can drive the research on efficient light harvesting devices. Here, we present a computational approach to the calculation of ET and EET rates in molecular DBA systems. Our approach to the calculation of EET couplings is based on a fully polarizable QM/MM/continuum approach. [2] This approach was extended to the electron transfer couplings, by using the Fragment Charge Difference scheme. [3] Both the energy transfer and electron transfer couplings were analyzed in terms of through-space and through-bond mechanisms. References [1] Albinsson, B.; Martensson, J.; J. Photochem. Photobiol. C: Photochem. Rev. 2008, 9, 138 [2] Caprasecca, S.; Curutchet, C.; Mennucci, B.; J. Chem. Theory Comput. 2012, 8, 4462 [3] Voityuk, A. A.; Rösch, N. J. Chem. Phys. 2002, 117, 5607 O P 1 9 | 28 INFLUENCE OF METALLIC UNDER-LAYER IN THE PERFORMANCE OF Cu2O PHOTOCATHODE & NOVEL METHOD FOR THE INVESTIGATION OF PHOTOACTIVE SEMICONDUCTOR MATERIALS USING CAVITY MICRO TIPS (C-ME) & SECM. Alberto Visibile,a Alessandro Minguzzi,a Alberto Vertova,a,b Sandra Rondinini. a,b a b Università degli Studi di Milano – Department of Chemistry; Via Golgi 19 –20133 Milano – Italy; Associate to C.N.R. – I.S.T.M., Via Golgi 19 – 20133 Milano – Italy e-mail: [email protected], A convenient approach to high purity hydrogen production is photo-electrochemical water splitting driven by solar energy. In this context, copper(I) oxide is an interesting p-type semiconductor with relatively low cost and the appropriate valence and conduction band energies. The literature reports a convenient method for preparing Cu2O based on the electrodeposition [1,2] onto Cr and Au nanolayers previously deposited on conducting glasses (e.g. FTO). In the present work, we aim at substituting these supports with the less hazardous and inexpensive Cu. Furthermore, a support made of electrodeposited Cu has the advantage of being prepared from the same deposition bath used for the deposition of the semiconductor, thus strongly simplifying the synthesis of the whole photoelectrode architecture. The results obtained in photocurrents with this metallic under-layer further overcome the ones obtained by the gold one. A larger dependence of photocurrents with deposition parameters of the metallic under-layer is also noticed. For this reason large matrix of sample were tested studying the influence of: temperature, amount of material, rate of deposition (current density), presence/absence of electrolyte convection, distance and dimension of the electrode both for metallic under-layer and for the semiconductor itself. In spite of the good values of recorded photocurrents, this material, as happens for other semiconductors in the framework of photo-electrochemical water splitting, is very unstable under work condition due to photo-degradation. In order to evaluate the photocurrent efficiency, a novel method using cavity micro-electrodes (CM-E) [3] and scanning electrochemical microscopy (SECM) is here presented. This system also allows to a rapid screening of semiconductor powders by quickly evaluating their photoactivity under working conditions. It uses SECM in Tip Generation- Substrate Collection (TG-SC) mode to determine the flux of product of interest (H2 in this case) with respect to the side reaction ones. References [1] Paracchino, A.; Brauer, J. C.; Moser, J. E.; Thimsen, E.; Grätzel, M. J. Phys. Chem. C 2012, 116, 7341 [2] Paracchino, A.; Laporte, V.; Sivula, K.; Grätzel, M.; Thimsen, E. Nature Materials 2011, 10, 456 [3] Morandi, S.; Minguzzi, A. Electrochem. Comm. 2015, 59, 100 29 | O P 2 0 AN ARTIFICIAL MOLECULAR PUMP POWERED BY LIGHT ENERGY Massimo Baroncini, Giulio Ragazzon, Serena Silvi, Margherita Venturi, Alberto Credi Photochemical Nanosciences Laboratory and Interuniversity Center for the Chemical Conversion of Solar Energy, Dipartimento di Chimica “G. Ciamician”, Università di Bologna, via Selmi 2, 40126 Bologna, Italy e-mail: [email protected] The bottom-up design, preparation and characterization of chemical systems that behave as molecular-scale machines and motors is a stimulating challenge of nanoscience [1]. The interest on this kind of systems arises from their ability to perform a (useful) function in response to chemical and/or physical signals. In this context, the use of light stimulation has several advantages, primarily because photons can be used to supply energy to the system (i.e., write) as well as to gain information about its state (i.e., read) [2]. Here we will describe investigations undertaken in our laboratories aimed at photo-inducing and -controlling large-amplitude molecular motions, both under thermodynamic and kinetic viewpoints, in multicomponent (supramolecular) species that comprise photoreactive units [3]. This work has recently culminated with the design, construction and operation of a system in which light irradiation causes the relative unidirectional transit of a nonsymmetric molecular axle through a macrocycle (see Figure) [4]. The device rectifies Brownian fluctuations by energy and information ratchet mechanisms and can repeat its working cycle under photostationary conditions (i.e., it shows autonomous energy dissipation). The conceptual and practical elements forming the basis of autonomous light-powered directed motion are implemented with a minimalist molecular design. As a matter of fact, this is the first example of a photochemically driven artificial molecular pump [5]. Systems of this kind can not only lead to radically new approaches in catalysis, materials science and medicine, but also disclose unconventional routes for the conversion of light energy into chemical energy. References [1] Balzani, V.; Credi, A.; Venturi, M. Molecular Devices and Machines – Concepts and Perspectives for the Nano World, Wiley-VCH: Weinheim, 2008. [2] Ceroni, P.; Credi, A.; Venturi, M. Chem. Soc. Rev. 2014, 43, 4068. [3] Avellini, T. et al., Angew. Chem. Int. Ed. 2012, 51, 1611; Baroncini, M.; Silvi, S.; Venturi, M.; Credi, A. Angew. Chem. Int. Ed. 2012, 51, 4223; Arduini, A. et al., J. Am. Chem. Soc. 2013, 135, 9924; Fasano, V. et al., J. Am. Chem. Soc. 2014, 136, 14245; Baroncini, M. et al., Nat. Chem. 2015, 7, 634. [4] Ragazzon, G.; Baroncini, M.; Silvi, S.; Venturi, M.; Credi, A. Nat. Nanotech., 2015, 10, 70. [5] Sevick, E. Nat. Nanotech. 2015, 10, 18; Ragazzon, G.; Baroncini, M.; Silvi, S.; Venturi, M.; Credi, A. Beilstein J. Nanotech., 2015, 6, 2096. O P 2 1 | 30 HYDROGEN UPGRADING WITH MEMBRANE REACTORS Adele Brunetti,a Alessio Caravella,b Lidietta Giorno,a Enrico Drioli,b Giuseppe Barbieri*,a a National Research Council – Institute on Membrane Technology (ITM-CNR), Via Pietro BUCCI, Cubo 17C, 87036 Rende CS, Italy b The University of Calabria – Dept. of Environment and Chemical Engineering, Via Pietro BUCCI, Cubo 44A, 87036 Rende CS, Italy e-mail: [email protected]; [email protected] In the hydrogen production, the energy carrier of the future, the syngas streams produced by reformers and/or coal gasification plants contain a large amount of H2 and CO needing to be upgraded. To this purpose, reactors using Pd-based membranes are largely investigated as they allow separation and recovery of a pure hydrogen stream. The high cost of the Pd-membranes is one of the main limitations for technology scaling up, thus, many researchers are now pursuing the possibility to use supported membranes with Pd-alloy layers as thinner as possible. The upgrading of syngas streams, i.e., the water gas shift reaction, was investigated in membrane reactor operated in the high (350-400°C) temperature range with selfsupported and ultra-thin (4 micron-thick) supported membranes [1-4]. Hydrogen production and recovery as well as the membrane reactor performance, e.g., CO conversion were evaluated as a function of operating conditions like temperature, pressure, gas hourly space velocity, feed molar ratio, sweep gas experimentally and by modelling analysis. Some results include CO conversion significantly higher than the thermodynamics upper limit of a traditional reactor even at a high gas hourly space velocity, a reaction volume of membrane reactor significant lower (<25%) than that of traditional reactor for achieving a conversion of 90% of the traditional reactor equilibrium conversion, etc. The concentration gradients generated by the permeation through the membrane and affecting the permeation itself were evaluated for both self–supported and supported membranes on both membrane sides using a computational fluid dynamic analysis. Then, concentration gradient coefficients were evaluated and used to correlate membrane reactor properties and operating conditions. Acknowledgement. The European Union, FP7 for research, technological development and demonstration is gratefully acknowledged for co-funding, under GA n. NMP3-LA-2011262840, the project “DEMCAMER – Design and Manufacturing of Catalytic Membrane Reactors by Developing New Nano-architectured Catalytic and Selective Membrane Materials” (www.demcamer.org) References [1] Brunetti, A.; Drioli, E.; Barbieri, G. Fuel Processing Technology, 2014, 118, 278-286, DOI: 10.1016/j.fuproc.2013.09.009 [2] Brunetti, A.; Caravella, A.; Fernandez, E.; Pacheco Tanaka, D.A.; Gallucci, F.; Drioli, E.; Curcio, E.; Viviente, J.L.; Barbieri, G. Int. J. of Hydrogen Energy, 2015, Vol. 40(34), 1088310893, DOI: 10.1016/j.ijhydene.2015.07.002 [3] Brunetti, A.; Sun Y.; Caravella, A.; Drioli, E.; Barbieri G. Int. J. Greenhouse Gases Control, 2015, 35, 18-29, DOI: 10.1016/j.ijggc.2015.01.021 [4] Caravella, A.; Melone, L.; Sun, Y.; Brunetti, A.; Drioli, E.; Barbieri G. Int. J. Hydr. Energy, 2015, submitted 31 | O P 2 2 ENERGY TRANSFER STUDIES IN HETEROBICHROMOPHORIC CALIXARENE SYSTEMS Irene Tosi,a Federica Faroldi,a Laura Baldini,a Francesco Sansone,a Cristina Sissa,a Francesca Terenziani,a Mariangela Di Donatob a Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze 17/A, 43124 Parma, Italy. b LENS, European Laboratory for Non-linear Spectroscopy, Via N. Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy. e-mail: [email protected] The synthesis and characterization of simple, well-controlled artificial systems able to mimic the fundamental processes occurring in the natural photosynthetic systems is currently an important goal considering the current, urgent need for clean and renewable energy sources. Studies on the energy and electron transfer processes taking place within these model systems, in fact, could allow for a more direct and precise understanding of the main factors determining the efficiency of photosynthesis. In this communication we report the synthesis and characterization of bi-chromophore units able to efficiently perform intramolecular energy transfer from the donor to the acceptor chromophore. These systems were obtained by covalently linking two different chromophores to a calix[4]arene scaffold. The possibility of choosing different calixarene conformations (i.e. cone and partial cone) allowed us to obtain analogous units where the donor and acceptor chromophores are kept at different distance. The dynamics of photo-induced energy transfer in these bi-chromophore units was studied by time-resolved absorption spectroscopy. Interestingly, we found that besides by exploiting a different calixarene conformation, the system performances can be further regulated by the appropriate choice of the external medium, which determines the particular conformation adopted in solution.1 Reference [1] Tosi, I.; Segado Centellas, M.; Campioli, E.; Iagatti, A.; Lapini, A.; Sissa, C.; Baldini, L.; Cappelli, C.; Di Donato, M.; Sansone, F.; Santoro, F.; Terenziani, F., ChemPhyChem. submitted for publication O P 2 3 | 32 EXPLOITING THE HCOOH/CO2 CYCLE FOR HYDROGEN PRODUCTION AND STORAGE BY HOMOGENEOUS CATALYSIS Federica Bertini,a Antonella Guerriero,a Irene Mellone,a Maurizio Peruzzini,a Luca Gonsalvi*,a a Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy. e-mail: [email protected] In the quest for sustainable routes to efficient hydrogen production and storage, liquid organic hydrogen carriers (LOHC) are nowadays considered as promising materials for this purpose. Among them, formic acid (FA, 4.4 % wt) affords H2 + CO2 gas mixtures by dehydrogenation in an “atom efficient” process. The CO2 (or bicarbonate) byproduct can be re-hydrogenated back to FA (or formate), affording a zero-carbon footprint cycle for hydrogen storage and release.[1] Among the methods to deliver such reactions, homogeneous catalysts based on precious and non-precious transition metal complexes have shown remarkable activities and are currently studied by many research groups worldwide.[2] In the past few years, our Research Unit at CNR-ICCOM has developed efficient catalytic processes for both FA dehydrogenation and NaHCO3 hydrogenation based on Ru-water soluble phosphines,[3] Ru(II) and Fe(II) polydentate phosphine complexes[4] working under mild conditions of pressure and temperature. An overview of principal results, including mechanistic studies, will be here presented. dehydrogenation - H2 production HCO2H/NR 3 HCO 2H (amine-free) HCO2 H/HCO2Na O cat. (0.1-0.01% mol) solventless or H 2O 60-90 °C H OH solvent, ∆T, pressure (CO < 0.02%) cat. = Ru(II) or Fe(II) [homog. catalyst] C H2 + CO2 conversion = 100% T ON > 10.000 (Ru) T ON > 6.000 (Fe) H2 + CO 2 cat. (0.05-0.1% mol) NaHCO3 solvent, H2 pressure, ∆T cat. = Ru( II) or Fe( II) hydrogenation - H 2 storage NaHCO2 max yield > 99% TON > 1.200 (Fe) CNR and ECRF are thanked for sponsoring this activity through projects EFOR and HYDROLAB-2.0, respectively. References [1] (a) Federsel, C.; Jackstell, R.; Beller, M. Angew. Chem. Int. Ed. 2010, 49, 6254; (b) Loges, B.; Boddien, A.; Gärtner, F.; Junge, H.; Beller, M. Top. Catal. 2010, 53, 902; (c) Grasemann, M.; Laurenczy, G. Energy Environ Sci. 2012, 5, 8171. [2] (a) Wang, W.-H.; Himeda, Y.; Muckerman, J. T.; Manbeck, G. F., Fujita, E. Chem. Rev. 2015 asap publication DOI: 10.1021/acs.chemrev.5b00197; (b) Dalebrook, A.; Gan, W.; Grasemann, M.; Moret, S.; Laurenczy, G. Chem. Commun. 2013, 49, 8735. [3] Guerriero, A.; Bricout, H.; Sordakis, K.; Peruzzini, M.; Monflier, E.; Hapiot, F.; Laurenczy, G.; Gonsalvi, L. ACS Catal. 2014, 4, 3002. [4] Bertini, F.; Mellone, I.; Ienco, A.; Peruzzini, M.; Gonsalvi, L. ACS Catal. 2015, 5, 1254. 33 | O P 2 4 SECOND GENERATION MOLECULAR SWITCHES BASED ON DIHYDROAZULENE/VINYLHEPTAFULVENE Martina Cacciarini*,a,b Martyn Jevric,b Jonas Elm,b Kurt. V. Mikkelsen,b Mogens Brøndsted Nielsenb a Department of Chemistry “Ugo Schiff”, via della Lastruccia 3-13, I-50019 Sesto Fiorentino (FI), Italy Department of Chemistry, Center for Exploitation of Solar Energy, Universitetsparken 5, DK-2100, Copenhagen, Denmark b e-mail: [email protected] The use of photochromic molecules in light-harvesting molecular devices for solar energy conversion and closed-cycle energy storage has become a hot topic in the last few years.1 Our previous experience with the photo/thermo-switch system dihydroazulene/vinylheptafulvene (DHA/VHF) prompted us to investigate its potential for this purpose. Upon irradiation, DHA undergoes a light-induced 10-electron retroelectrocyclization to VHF, and this is accompanied by a change of color from yellow to red.2 The thermal back-reaction to the parent DHA has a half-life of 218 min in CH3CN at 25 °C, and can be induced by means of mild Lewis acids. The system is accessible by an easy large-scale synthesis and can be functionalized at several positions, thereby tuning its photochromic characteristics, but very few studies have reported on modification of position 1, which is supposed to be the main responsible of the switching properties.3 This presentation will focus on the recent efforts to achieve second generation molecular switches by direct functionalization of position 1 on the parent DHA, either to harness and store solar energy, or to generate novel fast responsive photochromic materials. References [1] a) Kurcharski, T. J.; Tian, Y.; Akbulatov, S.; Boulatov, R. Energy Environ. Sci. 2011, 4, 4449; b) Moth-Poulsen, K. in Organic Synthesis and Molecular Engineering (Ed. M. B. Nielsen), Wiley, Hoboken, USA, 2014, pp. 179-196; c) Kucharski, T. J.; Ferralis, N.; Kolpak, A. M.; Zheng, J. O.; Nocera, D. G.; Grossman, J. C. Nature Chemistry, 2014, 441. [2] Mrozek, T.; Ajayaghosh, A.; Daub A. in Molecular Switches (Eds: B. L. Feringa), WileyVCH: Weinheim, 2001, pp 63-106. [3] a) Daub, J. ; Gierisch, S.; Klement, U.; Knöchel, T.; Maas, G.; Seitz, U. Chem. Ber., 1986, 119, 2631; b) Daub, J. ; Gierisch, S.; Knöchel T.; Salbeck, E.; Maas, G. Z. Naturforsch., 1986, 41b, 1151; c) Cacciarini, M.; Della Pia, E. A.; Nielsen, M. B. Eur. J. Org. Chem., 2012, 6064; b) Cacciarini, M.; Skov, A. B.; Jevric, M.; Hansen, A. S.; Elm, J.; Kjaergaard, H. G.; Mikkelsen, K. V.; Nielsen, M. B. Chem. Eur. J., 2015, 21, 7454. O P 2 5 | 34 A NEW 1,3,4-OXADIAZOLE-BASED HOLE TRANSPORT MATERIAL FOR EFFICIENT CH3NH3PBBR3 PEROVSKITE SOLAR CELLS: FACILE SYNTHESIS AND ENERGY LEVEL ALIGNMENT Stefano Carli1*, Juan Pablo Correa Baena2*, Giulia Marianetti3, Antonio Abate4, Stefano Caramori1, Michael Gräetzel4, Fabio Bellina5, Carlo Alberto Bignozzi1, Anders Hagfeldt2 1 Department of Chemistry and Pharmaceutical Sciences, University of Ferrara, Via Fossato di Mortara 17, 44121 Ferrara, Italy 2 Laboratory of Photomolecular Science, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne, CH-1015-Lausanne, Switzerland 3 Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy 4 Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne, CH-1015-Lausanne, Switzerland 5 Department of Chemistry and Industrial Chemistry, University of Pisa, Via Moruzzi 13, 56126 Pisa, Italy e-mail: [email protected] A new hole transport material based on the 1,3,4-oxadiazole moiety (H1), has been prepared through a one-step synthetic pathway1 starting from commercially available products. H1 was used as hole transport material (HTM) on CH3NH3PbBr3 (MAPbBr3)2 perovskite solar cells yielding a J-V hysteresis-free efficiency of 5.8%, while the reference material (Spiro-OMeTAD), in the same conditions, furnished a lower efficiency of 5.1% and a large J-V hysteresis. Thanks to its deep HOMO level, H1 is energetically well-aligned closer to the valence band of MAPbBr3 compared to the reference HTM. In addition, we show that the simplicity of the synthetic route of H1 can be easily extended to prepare other 1,3,4-oxadiazole based HTMs with the aim, for instance, of modulating the HOMO level by adjusting the substituents of the triarylamine unit. In addition, H1 shows a strong thermal stability and totally amorphous features (as evaluated by TGA and DSC), which represents another important step towards improving the long-term stability of perovskite solar cells3. References [1] Li, Y.; Michinobu, T. J. Polym. Sci. A Polym. Chem. 2012, 50, 2111 [2] (a) Schulz, P.; Edri, E.; Kirmayer, S.; Hodes, G.; Cahen, D.; Kahn, A. Energy Environ. Sci. 2014, 7, 1377. (b) Das, J.; Siram, R. B. K.; Cahen, D.; Rybtchinski, B.; Hodes, G. J. Mater. Chem. A 2015, 3, 20305. (c) Edri, E.; Kirmayer, S.; Kulbak, M.; Hodes, G.; Cahen, D. J. Phys. Chem. Lett. 2014, 5, 429. [3] Abate, A.; Paek, S.; Giordano, F.; Correa-Baena, J. P.; Saliba, M.; Gao, P.; Matsui, T.; Ko, J.; Zakeeruddin, S. M.; Dahmen, K. H.; Hagfeldt, A.; Grätzel, M.; Nazeeruddin, M. K. Energy Environ. Sci. 2015, 8, 2946. 35 | O P 2 6 VIRTUAL ORGANIZATIONS AT WORK: A PLANT FOR PRODUCING CARBON NEUTRAL CH4 Andrea Capriccioli,a Antonio Laganàb a b Enea, Via Fermi 145, Frascati, Italy. Dipartimento di Chimica, Via Elce di sotto 8, Perugia, Italy. e-mail: [email protected] Built on the activity scheme of the virtual organization COMPCHEM [1] under the guidance of the Innovative Computational Science Applications (ICSA) Association, the competitive collaboration between Enea (Frascati), R.P.C srl (Roma), Master-UP srl (Perugia), RDpower srl (Terni) carried out with the technical, financial and scientific support of the PLC-System srl (Acerra), the CNR Institute on Membrane Technology ITM (Rende), the Universities of Roma Tor Vergata, Roma 3 and Perugia has led to the assemblage of a prototype experimental apparatus named PROGEO producing CH4 out of CO2. In this way PROGEO targets two important challenges of the present energy market. Namely, it provides a technically efficient and cost effective solution to the capture of CO2 (by its transformation in synthetic and high value methane [2] and its storage as clathrate hydrate [3]) and a cheap and safe way for reusing the trapped energy either locally (“closed loop”) or remotely after transportation (“open loop”). Accordingly PROGEO can be used to better utilize renewable energy sources and to stabilize energy grids. Of the closed loop type is the use of PROGEO for electricity storage and CO2 valorization in small Thermoelectric Power Generation plants (ProGeo 500 kW) a modular unit with high flexibility, thanks to fast start-ups and shut-downs, while of the open loop type is the use of PROGEO for reducing to methane (to be used as fuel) the carbon dioxide produced by the fermentation of alcohols. The PROGEO process can be used also for enrichment of biogas. Moreover, following the recent transfer of the PROGEO 30 kW prototype apparatus from its original location at the PLC System to the University of Perugia within the frame of the ITN-EJD-642294 TCCM (Theoretical Chemistry and Computational Modelling) European project, the experimentation will be extended to the investigation of alternative catalytic technologies. References [1] Laganà, A.; Riganelli, A.; Gervasi, O. Lecture Notes in Computer Science 2006, 3980, 665. [2] Zhilyaeva, N.A.; Volnina, E.A.; Kukuna, M.A.; Frolov, V.M. Petrol. Chem. 2002, 42, 367. [3] Albertí, M.; Costantini, A.; Laganà, A.; Pirani, F. J. Phys. Chem. B, 2012, 116 (14), 4220 O P 2 7 | 36 CHEMICAL MODIFICATION OF CARBON NANOSTRUCTURES FOR ENERGY MATERIALS Teresa Gatti,a Patrizio Salice,a Bruno Pignataro,b Enzo Menna*a a b Dipartimento di Scienze Chimiche, Università di Padova, Padova, Italy. Dipartimento di Fisica e Chimica, Università di Palermo, Palermo, Italy e-mail: [email protected] The use of carbon nanostructures (CNSs) in energy related applications attracts large attention for different scopes, ranging from energy harvesting, to storage and release, thanks to their remarkable electrical/thermal conductivities and high aspect ratios, coupled to mechanical strength. The combination of CNSs, such as carbon nanotubes (CNTs), carbon nanohorns and graphene based materials (GBMs), with -conjugated polymers is particularly interesting for a possible use of the resulting polymer nanocomposites as active materials in photovoltaic devices,[1] light emitting diodes, field effect transistors, supercapacitors or fuel cells. The development of targeted functionalization processes can be a valid strategy to contrast CNS aggregation, while limiting the loss of electronic properties, and to tune the interactions between conductive polymers and CNSs. In an effort towards such a direction, we studied functionalization strategies to obtain CNS based functional materials that have been investigated for possible applications in the energy related fields. Among them, the preparation of photoactive heterojunction active layers based on blends of poly(3-hexylthiophene) (P3HT) and derivatized CNTs bearing on the external surface 4-(thien-2-yl)phenyl moieties, intended to improve their interaction with the thiophenebased polymer.[2] In this contest, we observed how an increase of functionalization degree affects the electronic communication of CNSs with P3HT. Our findings show that this is due not only to an increased density of defects, but probably also by the formation of multilayered organic structures (figure 1) that shield the carbon lattice. In fact, besides reaction conditions that can be finely tuned through flow chemistry, [3] we also investigated the influence of the relative amount of functional groups on morphology and properties of derivatives [4]. Figure 1. The effect of increasing functionalization degree on carbon nanostructure derivatives. We also functionalized CNTs and GBMs with 4-methoxyphenyl groups to be used in the preparation of polymeric blends in combination with P3HT and other conjugated polymers. Resulting nanocomposites have shown promising properties as hole transporting layers in perovskite solar cells [5] and are under investigation as electrode materials for capacitors. References [1] Cataldo, S.; Salice, P.; Menna, E.; Pignataro, B. Energy Environ. Sci. 2012, 5, 5919. [2] Salice, P.; Sartorio, C. P.; Burlini, A.; Improta, R.; Pignataro, B.; Menna, E. J. Mater. Chem. C 2015, 3, 303. [3] Salice, P.; Rossi, E.; Pace, A.; Maity, P.; Carofiglio, T.; Menna, E.; Maggini, M. J. Flow Chem. 2014, 4, 79. [4] Salice, P.; Fabris, E.; Sartorio, C.; Fenaroli, D.; Figà, V.; Casaletto, M. P.; Cataldo, S.; Pignataro, B.; Menna, E. Carbon 2014, 74, 73. [5] Casaluci, S.; Gatti, T.; Di Carlo, A.; Menna, E.; Bonaccorso, F. Proc. 2015 IEEE 15th International Conference on Nanotechnology (IEEE-NANO), in press. 37 | O P 2 8 NEW TRANSITION METAL COMPLEXES FOR CATALYTIC CO2 REDUCTION Federico Franco, Roberto Gobetto, Luca Nencini, Carlo Nervi University of Torino, Department of Chemistry, Via P. Giuria 7, 10125, Torino, Italy e-mail: [email protected], An efficient transformation of carbon dioxide into higher energy carbon products would make a remarkable impact on global economy, as an environmentally friendly decrease of the CO2 content in the atmosphere could be coupled with a sustainable approach to gain useful chemicals (e.g. CO, HCOOH and CH3OH).1 A possible approach to reduce the large overpotentials required for this multi-electron process is the use of organometallic molecular compounds, able to catalyze CO2 reduction. The development of suitable electrocatalysts, based on transition metal complexes, for the reduction of CO2 involves a number of requirements. The complexes have to be stable enough for isolation and purification. However, they have to be sufficiently reactive so that upon reduction they are capable of generating an empty coordination site needed for binding by carbon dioxide. Despite some interesting advances that have been made over the last few years, an efficient electrocatalytic conversion of carbon dioxide into more valuable chemicals remains a challenge.[1] Critical issues like selectivity, stability of the active species in solution, high operating overpotentials and intrinsic low catalytic activity toward CO2 reduction are the main technological barriers for the development of molecular catalysts suitable for industrial applications.[2] Polypyridyltype (and, more generally polyimine) ligands, which have extensive conjugated systems, not only stabilize transition metals in various oxidation states, but can also store multiple numbers of electrons in their π*-system. In addition, given the large number of ligands available in the literature, one can judiciously select the ligands and thus study their electronic effects in a deliberate fashion. Novel chlorotricarbonyl Re(I) complexes containing a highly fluorescent group, covalently attached to common polypyridyl ligands, show promising electro- and photocatalytic performances.[3] Nevertheless abundant and cheaper transition metals are commercially more attractive with respect to catalysts based on rare precious transition metals. In this perspective, the use of Group VI transition metals (Cr, Mo, W) with polypyridyl ligands as potential electrocatalysts for CO2 reduction is particularly attractive.[4] The availability of local proton sources is known to greatly enhance the selectivity and the redox catalytic activity for CO2 reduction to CO. Novel polypyridyl Mn(I) catalysts (e.g. [Mn(dhbpy)(CO)3Br] (dhbpy = 4-phenyl 6-(1,3-dihydroxybenzen-2-yl)-2,2'-bipyridine) containing two acidic OH groups in proximity of the purported metal binding site for CO2 redox catalysis show enhanced catalytic activity and clear mechanism pathway.[5] References [1] J. Ronge´, T. Bosserez, D. Martel, C. Nervi, L. Boarino, F. Taulelle, G. Decher, S. Bordiga and J. A. Martens, Chem. Soc. Rev., 2014, 43, 7963-7981. [2] J. M. Saveant, Chem. Rev., 2008, 108, 2348–2378. [3] F. Franco, C. Cometto, C. Garino, C. Minero, F. Sordello, C. Nervi,; R. Gobetto, , Eur. J. Inorg. Chem. 2015, 296-304. [4] F. Franco, C. Cometto,; F. Sordello,; C. Minero, L. Nencini, J. Fiedler, R. Gobetto, C. Nervi, ChemElectrChem, 2015, 2, 1372-1379. [5] F. Franco, C. Cometto, F. Ferrero Vallana,; F. Sordello, C. Minero, E. Priola,; C. Nervi, R. Gobetto, , Chem. Comm. 2014, 50, 14670-14673 O P 2 9 | 38 LUMINESCENT SOLAR CONCENTRATORS: HARNESSING THE BENEFITS OF NEW FLUOROPHORE/POLYMER MATRIX COMBINATIONS Matteo Sottile,a Pierpaolo Minei,a Francesca Martini,b,c Silvia Borsacchi,b,c Marco Geppi,a,c Giacomo Ruggeri,a,c Andrea Pucci*,a,c a Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, Pisa, Italy. Istituto di Chimica dei Composti OrganoMetallici (ICCOM) del CNR, UOS di Pisa, via G. Moruzzi 1, Pisa, Italy. c INSTM, UdR Pisa, Pisa, Italy. b e-mail: [email protected]. Sunlight concentration is one of the most promising paths toward the reduction of PV energy costs. As compared with classical optical concentrators, which are based on geometrical optics, luminescent solar concentrators (LSCs) show advantages like light weight, higher theoretical concentration factors, ability to work well with diffuse light and no need of sun tracking or cooling apparatuses.[1] However, in the current technology, the achieved power conversion efficiencies for LSC-PV systems are still low, with a maximum efficiency of 7.1%.[2] This is due to the many losses of such devices, both related to the physics of the phenomena involved and to a not-yetoptimized fluorescent system. In striving to contribute towards improved LSC outcomes, we proposed to switch from thermoplastic matrices, which represent the current state of the art, to more mechanically stable epoxy resins as bulk materials for LSCs. Heteroaromatic dyes such as Coumarin 6, Rhodamine B and Lumogen Red F350 were employed as compatible high quantum yield fluorophores for the crosslinked thermoset network. The combined Solid State NMR (SSNMR) and calorimetric investigations helped in determining the structural characteristics of the prepared slabs. The concentrating ability and the derived optical efficiencies of the epoxy-based LSCs were determined with a properly designed set-up[3] and compared to concentrators made of thermoplastic polymer matrix. Figure 1. Examples of epoxy-based LSCs based on high quantum yield compatible fluorophores References [1] Debije, M. Nature 2015, 519, 298. [2] Debije, M.; Verbunt, P. P. C. Adv. Energy Mater. 2012, 2, 12. [3] Carlotti, M.; Fanizza, E.; Panniello, A.; Pucci A. Solar Energy 2015, 119, 452. 39 | O P 3 0 A CHEMICAL VIEW AT A SUSTAINABLE PROCESS FOR BIOENERGY PRODUCTION Giuliana d’Ippolito, Laura Dipaquale, Angelo Fontana Istituto di Chimica Biomolecolare ICB-CNR, Via Campi Flegrei 34, 80078 Pozzuoli (Napoli), Italy e-mail: [email protected] Dark fermentation operated by the anaerobic thermophilic bacterium Thermotoga neapolitana is one of the most promising way for biological production of hydrogen in consideration of the high biogas evolution and versatility of the substrates that can be used to feed the cultures1. Complete and deep understanding of the characteristics and mutual cross-talk of the biochemical pathways related to hydrogen production is crucial to further improve rate and yield of the process. To this aim, we have recently reported an unprecendented pathway involved in the recycling of carbon dioxide by the hydrogen-producing bacterium Thermotoga neapolitana through the coupling of acetate and carbon dioxide with the concomitant production of lactic acid, without affecting hydrogen production2,3. The caphnophilic (CO2-requiring) pathway has been fully elucidated by using chemical approaches based on NMR and isotopically labelled tracers. The patented process offers the potential advantage of combining carbon capture, energy production from renewable source and synthesis of highly added value products such as lactic acid. The results concerning an effective and efficient integration of different processes for bioenergy production will also be discussed towards economically sustainable applications 4,5,6. References [1] d'Ippolito, G.; Dipasquale, L.; Vella, F.M.; Romano, I.; Gambacorta, A.; Cutignano, A.; Fontana A. Int J of Hydrogen Energy, 2010, 35, 2290. [2] d'Ippolito, G.; Dipasquale, L.; Fontana, A. ChemSusChem. 2014 7(9), 2678. [3] Dipasquale, L.; d'Ippolito, G.; Fontana, A. Int J of Hydrogen Energy, 2014 39 (10), 4857. [4] Dipasquale, L.; d’Ippolito, G.; Gallo, C.; Vella, F.M.; Gambacorta, A.; Picariello, G.; Fontana, A. Int J of Hydrogen Energy 2012, 37, 12250. [5] Dipasquale, L.; Adessi, A.; d'Ippolito, G.; Rossi, F.; Fontana, A.; De Philippis, R.; Appl Microbiol Biotechnol. 2015, 99(2), 1001. [6] d'Ippolito, G.; Sardo, A.; Paris, D.; Vella, F.M.; Adelfi, M.G.; Botte, P.; Gallo, C.; Fontana, A.; Biotechnol Biofuels. 2015, 22,8,28. O P 3 1 | 40 BLUE DYES FOR NEAR-INFRARED ABSORBING DYESENSITIZED SOLAR CELLS Alessio Dessì,*,a Massimo Calamante,a,b Alessandro Mordini,a,b Maurizio Peruzzini,a Adalgisa Sinicropi,c Riccardo Basosi,c Maurizio Taddei,c Lorenzo Zani, a Gianna Reginato. a a Istituto di Chimica dei Composti Organometallici (CNR–ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy b Dipartimento di Chimica “U. Schiff”, Università degli Studi di Firenze, Via della Lastruccia 13, 50019 Sesto Fiorentino (FI), Italy. c Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via A. Moro 2, 53100 Siena, Italy. e-mail: [email protected] Since their discovery in 1991,[1] Dye-Sensitized Solar Cells (DSSC) have been considered a very promising technology to convert solar energy in electric current due to their low cost of production, their innovative aesthetic properties and their easy integration in buildings and objects.[2] The dye, which can be a completely organic molecule, is the photoactive material and is considered the heart of a DSSC.[3] The introduction of an auxiliary acceptor group inside the classical D-π-A motif of the organic sensitizers can play a key role to achieve dyes with a very intense and broad light absorption spectrum and high incident photon-to-current conversion efficiencies.[4] Aiming to this goal, we designed two new D-A-π-A dyes containing as auxiliary acceptor group the (E)-3,3’-bifuranylidene-2,2’-dione,[5] a strong electron-withdrawing system which was firstly prepared in 1882.[6] The two new dyes have been synthesized and characterized, showing an intense blue color in solution and when adsorbed on a TiO2 electrode, a broad absorption of the red/near-infrared light between 500 and 800 nm and right electrochemical potentials for a proper use in DSSCs. References [1] O‘Reagan, B.; Grätzel, M. Nature 1991, 353, 737. [2] Dye-sensitized solar cells (Ed.: K. Kalyanasundaram), EPFL Press, Lausanne 2010. [3] Hagfeldt, A.; Boschloo, G.; Sun. L.; Kloo, L.; Petterson, H. Chem. Rev. 2010, 110, 6595. [4] Wu, Y.; Zhu, W. H. Chem. Soc. Rev. 2013, 42, 2039. [5] Kingsberg, E. Chem. Rev. 1954, 54, 59. [6] Von Pechmann, H. Ber. 1882, 15, 885. 41 | O P 3 2 ELECTRIC AND THERMAL ENERGY FROM BIOETHANOL: PROCESS INTENSIFICATION BY USING DILUTED FEED Ilenia Rossetti,* Matteo Compagnoni Dip. Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milan, Italy e-mail: [email protected] Bioethanol attracted growing interest as raw material for the production of hydrogen. The latter can be successfully used to feed fuel cells with the aim of combined heat and power (CHP) cogeneration. A demonstrative project has been carried out c/o our Dept. [1] by running an integrated CHP unit with residential size, i.e. 5 kWel + 5 kWth. It was constituted by 6 integrated reactors, connected in series, fed with bioethanol and water, to produce reformate gas (prereformer and steam reformer) and to accomplish gas purification from CO (high- and low-temperature water gas shift reactors and two methanators). The purified reformate is suitable to feed a PEM fuel cell with the above mentioned power output. The aim of this work was to focus on process intensification, to achieve an economically sustainable solution. This was done at first by identifying the effect of bioethanol concentration on process output and proposing suitable means to achieve bioethanol purification. This is particularly straightforward because second generation bioethanol is nowadays proposed as fuel or as blending agent for gasoline, thus requiring deep dehydration. However, if used as feed for steam reforming, much lower concentration is needed, allowing to limit distillation/dehydration cost, which account for 50-80% of bioethanol production expenses [2,3]. Process layout has been revised by comparing different possible schemes, compared as for heat and power duty (input) and output. Different solutions to account for energy input to the reformer have been also compared. Accordingly, different options for the purification of raw bioethanol beer have been compared, in order to meet the required specifications and to limit the cost of the reformer feed. The effect of the purity of the resulting bioethanol stream on reformer performance has been also experimentally addressed. As well, the effect of reactor temperature was considered, and this was set at the minimum level to guarantee optimal product yield, suitable catalyst durability and minimum heat input to the reactor. Process simulation has been carried out by using the Aspen Plus software and economic assessment of the solutions proposed has been carried out by using the Aspen ONE cost evaluation tool. References [1] Rossetti, I.; Biffi, C.; Tantardini, G.F.; Raimondi, M.; Vitto, E.; Alberti, D. Int. J. Hydrogen Energy, 2012, 37, 8499. [2] Rossetti, I.; Compagnoni, M.; Torli, M. Chem Eng. J., 2015, 281, 1024. [3] Rossetti, I.; Compagnoni, M.; Torli, M. Chem Eng. J., 2015, 281, 1036. O P 3 3 | 42 BIS-PHENANTHROLINE COPPER COMPLEXES IN IODINEFREE ELECTROLYTES FOR DSSCs Mirko Magni,*,a Alessia Colombo,a Roberto Giannuzzi,b Claudia Dragonetti,a Maria Pia Cipolla,b Stefano Caramori,c Carlo Alberto Bignozzi,c Dominique Robertoa, Michele Mancab a Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, Milano, Italy. Center for Biomolecular Nanotechnologies – Fondazione Istituto Italiano di Tecnologia, via Barsanti snc,Arnesano, Italy. c Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, via Fossato di Mortara 17, Ferrara, Italy. b e-mail: [email protected] Dye-sensitized solar cells, DSSCs, are photoelectrochemical devices well contextualized within the global commitment for the progressive increase of the percentage of electric energy produced by renewable resources. This technology should free us from all problems and risks related to fossil fuels exploitation, in favor of the ubiquitous and practically inexhaustible sunlight. Since the milestone paper of Graetzel and O’Regan [1], dye engineering has been for many years the unique task of scientists to improve the photon-to-current conversion efficiency, PCE, of cells. Only in the last decade the crucial role played by redox mediators has emerged, attracting attention mainly on tris(diimine) cobalt complexes capable of raising PCEs up to 14%. In the frame of iodine-free electrolytes, our group has proposed novel homoleptic 1,10phenanthroline copper complexes [2,3] able to significantly exceed the unique effective literature benchmark proposed to date, based on neocuproine ligands [4]. In this contribution we will present our results dealt with the study of how ligand substituents affect the electrochemical [5] and optical features of this class of complexes so as to reduce light harvesting competition with dye and to overcome kinetic dichotomies active in DSSCs. These “structure vs activity maps” have been then exploited to choose a selected ensemble of compounds to be tested in DSSCs as electron shuttles and to rationalize their photoelectrochemical performances. Particular attention was also dedicated to select a cathode material able to minimize the overpotential for the mediator regeneration reaction. As a result we have proposed a convenient Cu-based redox couple based on bulky 2mesityl-4,7-dimethyl-1,10-phenanthrolines that, in combination with two completely different dyes (i.e. a Ru-based [2] and an organic one [3]), has more than doubled the PCE of cells filled with the benchmark neocuproine-based shuttles and has reached values even slightly higher than a equimolar I–/I3– control electrolyte [3]. References [1] O’Regan, B.; Graetzel, M. Nature 1991, 353, 737. [2] Colombo, A.; Dragonetti, C.; Magni, M.; Roberto, D.; Demartin, F.; Caramori, S.; Bignozzi, C. A. ACS Appl. Mater. Interfaces 2014, 6, 13945. [3] Magni, M.; Giannuzzi, R.; Colombo, A.; Dragonetti, C.; Cipolla, M. P.; Caramori, S.; Grisorio, R.; Suranna, G. P.; Bignozzi, C. A.; Roberto, D.; Manca, M. J. Phys Chem. Lett. submitted. [4] Bai, Y.; Yu, Q.; Cai, N.; Wang, Y.; Zhang, M.; Wang, P. Chem. Commun. 2011, 47, 4376. [5] Magni, M.; Colombo, A.; Dragonetti, C.; Mussini, P. Electrochimica Acta 2014, 141, 324. 43 | O P 3 4 IMPACT OF SULPHUR ON DRY REFORMING OF BIOGAS OVER A Rh/Al2O3 CATALYST Stefano Cimino, Luciana Lisi, Gabriella Mancino Istituto Ricerche sulla Combustione - CNR, P.le V. Tecchio 80, 80125 Napoli, Italy. e-mail: [email protected] Catalytic dry reforming (DR) is a potential option to valorize and upgrade biogas [1,2], a mixture of methane and carbon dioxide produced from the anaerobic microbial digestion of biomass. The syn-gas obtained by DR has a low H2/CO ratio (≤1), which is suitable for further processing in the synthesis of valuable liquid fuels and oxygenated chemicals. Literature reports agree that Rh-based catalysts can provide outstanding syn-gas yields with carbon-free operation [3,4], but, quite surprisingly, only few studies have reported on the effect of sulphur during the dry reforming of methane on Rh, where the situation is further complicated by the process tendency to give carbon deposition, and they show contradictory results. Therefore, in this work we set out to investigate the impact of sulphur poisoning during dry reforming (DR) of methane with CO2 over a Rh/γAl2O3 catalyst by adding up to 30 ppmv of SO2 or H2S to the feed (CH4/CO2/N2=1/1/2) at reaction temperatures in the range 800 - 900 °C. As low as 1 ppmv of sulphur in the feed adversely affected the H2 and CO yields, and S-poisoning reached a saturation level for contents ≥ 10 ppmv, independently from the type of S-bearing compound. The impact of S addition on the RWGS reaction, occurring simultaneously to DR, was also investigated under steady state operation. Transient poisoning experiments showed a rapid drop of syn-gas production and a corresponding increase in the temperature level, suggesting that sulphur directly bonded to Rh active sites. An increase of coke formation on the catalyst was detected with respect to S-free conditions, and this effect was studied by Raman spectroscopy and thermogravimetric analysis. Sulphur inhibition was reversible and the Rh-based catalyst slowly recovered its initial activity after the removal of sulphur from the feed. Acknowledgements. The authors acknowledge the financial support by Ministero per l'Istruzione, l'Università e la Ricerca (MIUR) – Italy (PRIN2010 H7PXLC - Innovative processes for the conversion of algal biomass). References [1] Surendra, K.C.; Takara, D.; Hashimoto, A. G.; Khanal, S. K. Renew. Sustain. Energy Rev. 2014, 31, 846. [2] Kohn, M.P.; Castaldi, M.J.; Farrauto, R.J. Appl. Catal. B. 2014, 144, 353. [3] Cimino, S.; Torbati, R.; Lisi, L.; Russo, G. Appl. Catal. A 2009, 360, 43. [4]Chakrabarti, R.; Colby, J.L.; Schmidt, L.D. Appl. Catal. B 2011,107, 88. O P 3 5 | 44 DYE-SENSITIZED SOLAR CELLS: AN EXAMPLE OF A PHOTOELECTROCHEMICAL DEVICE IN ARCHITECTURE. Isabella Zama,a Luigi Armiento,a Valerio Borzatta,a Giacomo Gorni,a Christian Martelli,a Simone Vierucci,a a Daunia Solar Cell S.r.l., subsidiary of TRE S.p.A. Tozzi Renewable Energy, via Zuccherificio 10, 48123 Mezzano (RA), Italy. e-mail: [email protected], Dye-sensitized Solar Cells (DSSC) [1] are an emerging technology for the Building Integrated Photovoltaics market thanks to their semi-transparency and the relative easy fabrication. Due to the complexity of their hybrid organic and inorganic nature, a transversal development on materials, processes and final application is needed to be competitive in an industrial environment: the best compromise between efficiency, transparency, stability, cost and process sustainability must be pursued. DSSC is a photo-electrochemical device containing an aggressive iodine-based liquid electrolyte, so a glass-on-glass assembly with long-term stability of the sealing is hard to achieve with a polymer sealant. Glass frit sealant is a good candidate to guarantee the insulation of internal components from environmental agents [2]. The DSSC photoanode is composed by a porous semi-conductor layer, typically titanium dioxide in its anatase form, with anchored dye molecules able to capture a portion of sunlight [3]. To guarantee the semi-transparency of the layer and, at the same time, to provide a large surface area to grab the dye, the titanium dioxide layer must ensure a well dispersed nanostructure, even after thermal treatment. We developed a lead-free glass frit with low softening point and proper coefficient of thermal expansion to have an optimal compatibility with the glass substrate: this allows an optimal resistance to humidity and temperature for over 1000 hours @85°C of DSSCs modules with area up to 900 cm2. Furthermore, the sealant is inert to iodineiodide redox couple. A nano-titania screen printable paste has been optimized and a semitransparent crack-free layer after thermal treatment was obtained up to 10 µm. Advanced ceramic materials – glass frit and nano-titania – were successfully applied in DSSC. Both materials were deposited through a low cost screen-printing technique, showing a potential for process scalability. Pleasing aesthetic appearance in terms of transparency and uniformity was obtained, together with good efficiency and stability. Several DSSC modules, 30x30 cm2 each, have been integrated into demonstrating prototypes, i.e. a double glazed window for building integration and a photovoltaic tables to recharge portable devices. References [1] O’Regan B.; Grätzel M. Nature 1991, 353, 737-740. [2] Sastrawan R.; Beier J.; Belledin U. Hemming S.; Hinsch A.; Kern R.; Vetter C.; Petrat F.M.; Prodi-Schwab A.; Lechner P.; Hoffmann W. Prog. Photovolt: Res. Appl. 2006; 14:697– 709, 2006, 14, 697-709. [3] Anders Hagfeldt A.; Boschloo G.; Sun L.; Kloo L.; Pettersson H. Chem. Rev., 2010, 110, 6595-6663 45 | O P 3 6 BIOLOGICAL CONSTRAINTS IN THE SCALE-UP OF PHOTOBIOLOGICAL HYDROGEN PRODUCTION Giuseppe Torzillo, Elefterios Touloupakis Institute of Ecosystem Study, National Research Council of Italy. Via Madonna del Piano 10, Sesto Fiorentino, Florence, Italy The use of solar light is mandatory if the goal in question is to scale-up photobiological hydrogen production to an industrial level. A number of photobioreactor designs are being proposed, mostly in the mass culture of microalgae for biodiesel production, while information on the scale-up of H2 production, in particular outdoors, is still very limited . One of the most important aspects affecting the culture performance outdoors is the problem of light saturation. To circumvent this problem, we have designed and devised a new photobioreactor, one which enables a more uniform distribution of light over the reactor surface. To attain this goal, the tubular reactor was immersed in a lightscattering silica nanoparticle suspension. The reactor performance was assessed by means of a culture of Chlamydomonas reinhardtii under sulfur starvation conditions. Recently, another novel photobioreactor (1350 L) was devised and constructed by our group, for the outdoor cultivation and hydrogen production with the cyanobacterium Synechocystis PCC 6803. The reactor was designed to promote the “light dilution effect”, which should enable the cells to use solar light with higher efficiency, and should also reduce the risk of photoinhibition. The biomass yield of the culture reached about 25 g/m2/day. One of the serious problems that arose during the cultivation of Synechocystis outdoors was the susceptibility of the cells to predation by various type of protozoa and other class of algae (e.g., Chrysophyceae). Practical methods for preventing contamination in large-scale PBR have been successfully tested. O P 3 7 | 46 WATER-BASED ELECTROLYTES IN HYBRID SOLAR CELLS: FROM LIQUID TO GEL FORMULATIONS Simone Galliano,a Federico Bella,b Claudia Barolo*,a Claudio Gerbaldi,b Guido Viscardib a Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di Torino,Via Pietro Giuria 7, 10125-Torino, Italy b GAME Lab, Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca Degli degli Abruzzi 24, 10129-Torino, Italy e-mail: [email protected] Dye sensitized solar cells (DSSCs) with high performances have been fabricated mainly with organic solvent-based liquid electrolytes. [1] However, these solvents not only have high vapor pressure, but they are often toxic and flammable. In the last few years, the idea of moving towards a water-based system clearly emerged. [2] DSSCs fabricated with water-based electrolytes may offer reduced costs, non-flammability and environmental compatibility, but the presence of water in the cell may reduce the long term stability as well as the photovoltaic performance. For this reason, in recent years, an increasing number of research articles has been published in this direction and new dyes, electrodes and electrolyte components are continuously proposed.[3] In this work, the study of different truly aqueous electrolytes is presented and a chemometric approach, useful to investigate and optimize their efficiency and stability, is effectively demonstrated. A few curious and anomalous behaviors observed in the literature and in our laboratories are investigated for this class of electrolytes. Moreover the development of a series of novel aqueous gel electrolytes based on natural polymers is also discussed as well as their interesting photovoltaic characteristics. References [1] Mathew, S.; Yella. A.; Gao. P.; Humphry-Baker, R.;. Curchod, B. F. E.; Ashari-Astani, N.; Tavernelli, I.; Rothlisberger, U.; Nazeeruddin, M. K.; Grätzel, M. Nat. Chem. 2014, 6, 242. [2] Xiang, W.; Huang, F.; Cheng, Y.-B.; Bach, U.; Spiccia, L. Energy Environ. Sci., 2013, 6, 121. [3] F. Bella, F.; Gerbaldi, C.; Barolo, C.; Grätzel, M. Chem. Soc. Rev. 2015, 44 (11), 3431. 47 | O P 3 8 CHARACTERIZATION OF AN YEAST BASED MICROBIAL FUEL CELL Ruggero Rossia, Mattia Cavinaa, Andrea Fedriguccia, Andrea Pretia, Leonardo Settia a Dept. of Industrial Chemistry «Toso Montanari» – University of Bologna, Bologna, Italy e-mail: [email protected] Biomasses represent one of the most used renewable vector since permit to produce electric and thermic energy towards the traditional combustion technologies. However, for domestic or industrial wastewater, the energy contained in the dissolved organic fraction can be difficultly exploit caused by the high water content. Microbial fuel cells (MFCs) are devices that convert the chemical energy of naturally available organic substrates directly into electricity by using different microorganisms as bio-microreactors. The organic matter is oxidized through the catabolic metabolism of the microorganisms, and the gained electrons are then transferred to the anode. The electrons that reach the anode pass through the external load circuit to the cathode. The result is the production of an electrical current using renewable resources such as the organic substrates present in wastewater of domestic or industrial origin. MFCs have clear advantages of operation at mild reaction conditions, cost effective and biotechnology based wastewater treatment with reduced sludge formation coupled with energy generation over chemical fuel cells that use highly reactive fuels and severe operating conditions. In our findings, a common baker’s yeast such as Saccharomyces cerevisiae was used in a laboratory scale dual chamber microbial fuel cell operating under batch mode with salt bridge as electrolyte. Glucose and methylene blue were used as the carbon source and the electronophore (mediator) in the anode compartment, respectively. The system was started in anaerobic conditions with initial glucose concentration of 5gl-1. The rate of substrate consumption in the anodic compartment indicated that Saccharomyces cerevisiae had a huge potential to generate electrons (1). The aim of our studies is to investigate the mediator's influence on the electrode–yeast interactions with respect to improvement of the biofuel cell's performance. The bioelectrochemical reactor was studied with different operative conditions as well as bioreactor design of the anode chamber. The maximum voltage generated in the microbial fuel cell was 479 mV and the maximum power output was 51.2 mWm-2 without application of external load, using hydrogen peroxide as electron acceptor in the cathode chamber. References [1] Rossi R., Fedrigucci A., Setti L., Characterization of electron mediated microbial fuel cell by Saccharomyces cerevisiae, Chemical Engineering Transactions 2015, 43, 337-342. DOI: 10.3303/CET1543057. O P 3 9 | 48 2,5-DIARYL SUBSTITUTED AZOLES AS PROMISING DYES FOR LUMINESCENT SOLAR CONCENTRATORS Giulia Marianetti, 1 Pierpaolo Minei,2 Vincenzo Barone,1 Andrea Pucci,2 Fabio Bellina2 1 2 Scuola Normale Superiore. Piazza dei Cavalieri 7, 56126 Pisa, Italy Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, 56124 Pisa, Italy e-mail: [email protected] Over the last three decades lot of interest has been devoted to light harvesting technologies. Recent findings on global warming and energy nonrenewable resources push us to alternative means of storing energy.[1] Sunlight stands indeed as an ideal asset to take advantage of. In this insight Luminescent Solar Concentrators (LSCs) represent a way to decrease the cost of solar photovoltaics.[2,3] LSC devices usually consist in a thin slab of transparent material (glass or polymer) doped with a fluorescent dye. Upon solar irradiation, a fraction of the emitted light, through means of internal reflection, is collected at the edges of the device where photovoltaic cells are located. Compared to traditional concentrators, which make use of mirrors and lenses, these devices show numerous advantages, such as theoretical higher concentration factors, the ability to work with both diffuse and incident light and no need for tracking devices or cooling apparatuses.[2] Organic fluorescent dyes bearing π-conjugated electrondonor and -acceptor moieties exhibit intramolecular charge-transfer (ICT) properties,[4] and can therefore show the optical properties required by LSCs such as high quantum yield and high Stokes shift.[3] On account of this, the present communication will discuss the synthesis and UV-Vis characterization of a set of novel symmetrical push-pull azole-based dyes of general structure 1. These compounds are characterized by a central 1,3-azole 2,5 substituted with two aromatic rings bearing electron withdrawing (EWG) groups. Remarkably, the introduction of an heteroaromatic ring usually improves the thermal and chemical stability and the overall polarizability.[4] Figure 1: General structure of push-pull azole-based dyes 1. The 2,5-diaryl substituted azoles 1 were prepared through a robust synthetic pathway involving a palladium and copper-promoted direct C-H arylation reaction as key step. We took into account the effect of the peripheral electron poor funtionality as well as the nature of the central heteroaromatic core, comparing 1-methylimidazole, thiazole and oxazole. In order to rationalize the experimental results we carried out TD-DFT studies, that allowed us to proper understand the charge tranfer occuring during the electronic transition. After selecting the best fluorophore for our aim, we investigated its efficiency in an LSC prototype. References [1] Houghton, J. Global Warming (3rd ed.). Cambridge University Press, 2005. [2] van Sark, W.G.J.H.M EPJ. Web of conferences 2012, 33, 02003. DOI: 10.1051/epjconf/20123302003 [3] Rowan, B.C.; Wilson, L.R.; Richards, B.S. Ieee Journal Of Selected Topics In Quantum Electronics 2008, 14, 1312. [4] Bures, F. RSC Adv. 2014, 4, 58826. 49 | O P 4 0 Pd/C-CeO2 ANODE CATALYST FOR HIGH PERFORMANCE PLATINUM FREE ANION EXCHANGE MEMBRANE FUEL CELLS Hamish A. Miller,a Alessandro Lavacchi,a Francesco Vizza,a Marcello Marelli,c Francesco Di Benedetto,f Francesco D’Acapito,g Yair Paska,b Miles Page,b Dario R. Dekeld,e a Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze, Italy. b CellEra, Caesarea Business and Industrial Park, Caesarea, 30889, Israel. c Istituto di Scienze e Tecnologie Molecolari (ISTM-CNR) via Camillo Golgi 19, 20133 Milano. d The Wolfson Department of Chemical Engineering, Technion – Israel Institute of Technology, Haifa, 3200003, Israel. e The Nancy & Stephan Grand Technion Energy Program (GTEP), Technion – Israel Institute of Technology, Haifa 3200003 Israel. f Department of Earth Sciences, Università di Firenze, Via G. La Pira, 4, 50100 Firenze, Italy. g CNR-IOM-OGG c/o ESRF, 71, Avenue des Martyrs, CS, 40220 Grenoble, Cédex 9, France. e-mail: [email protected] The fuel cell is the best device for converting cleanly the chemical energy of hydrogen into electricity on demand with the only byproducts water and heat. State of the art low temperature proton exchange membrane fuel cells (PEM-FCs) are compact, yet high power-density systems ideal for automotive applications. The removal of costly platinum from PEM-FCs is one of the most commonly cited objectives for researchers in the field. Here, we describe a platinum free anion exchange membrane fuel cell (AEM-FC) that employs nanostructured Pd anode and Ag cathode electrocatalysts. AEM-FC tests run on dry hydrogen and pure air show peak power densities of more than 500 mW cm-2. Such high power output is due to a nanoparticle Pd anode catalyst with a composite support made from Vulcan XC-72 carbon and CeO2 that exhibits enhanced kinetics for hydrogen oxidation in alkaline media. O P 4 1 | 50 CONJUGATED POLYMERS FOR SOLAR CELLS INCORPORATING THE DITHIENOSILOLE UNIT Francesca Parenti,a Franceso Tassinari,a Alice Cugini,a Luisa Schenetti,b Pasquale Morvillo,c Rosa Ricciardi,c Adele Mucci,a* a Università di Modena e Reggio Emilia, Dipartimento di Scienze Chimiche e Geologiche, Via Campi 103, 41125 Modena, Italy. b Università di Modena e Reggio Emilia, Dipartimento di Scienze della Vita, Via Campi 103, 41125 Modena, Italy. c ENEA, SSPT-PROMAS-NANO, Piazzale E. Fermi 1, 80055 Portici (NA), Italy. e-mail: [email protected], Polymer Solar Cells (PSC) are widely studied as low cost, light weight and flexible alternative to silicon-based solar cells.1 The polymers suitable for this purpose should possess good solubility and filming properties and extended π-conjugated systems with high absorption coefficients, UV–Vis-NIR spectra ideally matching the solar spectrum,2 high hole mobility, and HOMO–LUMO energy levels suitable to be coupled with the acceptor species, such as fullerene derivatives.3 One of the newest monomeric units that can be used to build conjugated polymers for PSC is functionalized dithienosilole (Scheme 1). This contribution will deal with the synthesis and properties of two different low band gap copolymers containing dithienosilole alternated to thienothiophene or to substituted bithiophene. Scheme 1 References [1] Günes, S.; Neugebauer H.; Sariciftci, N.S. Chem. Rev. 2007, 107, 1324; Chidichino, G.; Filippelli, L. Int. J. Photoenergy 2010, 2010, Article ID 123534, doi: 10.1155/2010/123534; Li, G.; Zhu, R. and Yang Y. Nature Photon 2012, 6, 153; Xu, T.; Yu, L. Mater. Today, 2014, 17, 11. [2] Kroon, R.; Lenes, M.; Hummelen, J.C.; Blom, P.W.M.; de Boer, B. Polym. Rev. 2008, 48, 531–582. [3] Gadisa, A.; Svensson, M.; Andersson, M.R.; Inganäs, O. Appl. Phy. Lett. 2004, 84, 1609; Morvillo, P.; Bobeico, E. Sol. Energ. Mater. Sol. Cells 2008, 92, 1192. 51 | O P 4 2 SUGAR-BASED IRON-DOPED N-CARBONS FOR OXYGEN REDUCTION REACTION. Stefania Marzoratia, Marco Renzib, Francesco Nobilib, Mariangela Longhia,*, a Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133 Milano, Italy Università degli Studi di Camerino, Scuola di Science e tecnologie – Sezione Chimica Via S. Agostino 1, 62032 Camerino (MC), Italy b e-mail: [email protected] Fuel cells for low temperature applications are the subject of intensive research because they could reduce consumption of primary fossil fuels and greenhouse gas emissions. However, performances of these devices are severely limited by the kinetics of the oxygen reduction reaction (ORR) at the cathode, so that the use of high-cost catalysts, such as Pt, is so far mandatory. Although catalytically optimal, Pt catalysts suffer drawbacks such as formation of poisoning surface Pt-oxides and particle coarsening (by dissolution/re-precipitation, Ostwald ripening), that cause loss of both active surface area and activity. Other negative aspects have economic origin due to the metal natural scarcity and cost. A very interesting research challenge is to find an alternative nonprecious, though less catalytically performing, catalyst. Among others, nitrogenmodified carbons doped with non-precious transition metal centres, typically iron, are of interest because of reduced costs of precursors and easiness by which composition and morphology can be modulated by preparation. In this work we present some results on oxygen reduction reaction by a series of Pt-free catalysts obtained by pyrolysis of guanidine-based nitrogen compounds/sugar mixtures in the presence of a metal salt and a templating agent. Catalysts were characterized by physical, chemical and electrochemical methods. Results are presented in terms of the influence that precursors nature exerts on oxygen reduction onset potential, presence of defined limiting current and reaction mechanism. They are characterized by a well-defined limiting current, an onset potential approaching Pt ORR starting potential and a number of exchanged electrons n>3.9. An attempt of explanation of different electrocatalytic behavior obtained varying the nature of precursor is also done. O P 4 3 | 52 THIO-ETHYLPORPHYRAZINE NANOHYBRIDS WITH SINGLE-WALL CARBON NANOTUBES AND GRAPHENE FOR PHOTOINDUCED ELECTRON TRANSFER S. Belvisoa, E. Santoroa, F. Lelja, A. Capassob, L. Najafib, A. E. Del Rio Castillob, S. Casalucic, T. M. Brownc, A. Di Carloc, F. Bonaccorsob a Dipartimento di Scienze - Università della Basilicata, via dell'Ateneo Lucano 10, I-85100, Potenza,IT. Graphene Labs, Istituto Italiano di Tecnologia, I-16163, Genoa , IT. c CHOSE (Centre for Hybrid and Organic Solar Energy), Dipartimento di Ingegneria Elettronica, Università degli Studi di Roma “Tor Vergata”, Via del Politecnico 1, I-00133, Rome, IT. b e-mail: [email protected], Tetrapyrrole macrocycles can in principle both absorb light in the visible range and transfer/accept photogenerated electrons,1 thus being exploitable as light acceptors in organic photovoltaics (OPVs). Photoactive hybrid structures made of phthalocyanines or porphyrins with single-wall carbon nanotubes (SWNTs) and graphene flakes were recently investigated.2 The linkage between the macrocycle and the carbon surface is due to either covalent bonds or noncovalent π-π interactions often mediated by pyrene units. In the quest for novel light acceptors for efficient OPVs, we focused on pyrene derivatives of thio-alkylporphyrazines, tetrapyrrole macrocycles widely used in nonlinear optic materials,3 but never studied before in OPV. We first synthesized the new pyrene-substituted thio-ethylporphyrazine 1 (Figure) and characterized it by spectroscopic and electrochemical measurements. The structural and electronic properties of 1 were also investigated by DFT and TDDFT computations. Compound 1 was then mixed with SWNTs and graphene flakes (prepared by solution processing) to create two hybrid structures, subsequently characterized by microscopy and optical spectroscopy. Photoluminescence analyses have shown emission quenching in both hybrid structures, indicating the occurrence of charge transfer between 1 and the carbon nanomaterials. Preliminary electrochemical measurements on the hybrid structures were carried out in dark and under light illumination to assess the photocurrent generation. The pyrene unit in 1 is found to effectively promote the electronic interaction between the macrocycle and the carbon nanomaterials, thus promoting charge transfer, and a photocurrent. Figure: structure of compound 1 References [1] Calogero, G.; Bartolotta, A.; Di Marco, G.; Di Carlo, A.; Bonaccorso, F. Chem. Soc. Rev. 2015, 44, 3244. [2] Roth, A.; Ragoussi, M.-E.; Wibmer, L.; Katsukis, G.; de la Torre, G.; Torres, T.; Guldi, D. M. Chem. Sci. 2014, 5, 3432. [3] Belviso, S.; Amati, M.; Rossano, R.; Crispini, A.; Lelj, F. Dalton Trans. 2015, 44, 2191. 53 | O P 4 4 NANOSCALE IONIC MATERIALS FOR ADVANCED NANOCOMPOSITES IN HIGH TEMPERATURE PROTON EXCHANGE MEMBRANE FUEL CELLS Isabella Nicotera,*,a Cataldo Simari,a Lamprini G. Boutsika,b Apostolos Enotiadis,b Georgia Charalambopoulou,b Theodore A. Steriotis,b Cesare Oliviero Rossi a a Department of Chemistry and Chemical Technologies, University of Calabria, via P. Bucci, Cubo 14D, 87036 Rende, CS, Italy b National Center for Scientific Research “Demokritos”, 15310, Ag. Paraskevi Attikis, Athens, Greece email: [email protected] The continuous improvement of Polymer electrolyte membrane Fuel Cell (PEMFC) is of top priority for the development of next generation fuel cell with lower cost and increased durability/efficiency. Although significant efforts have been made towards PEMFCs commercialization, there are still technical challenges such as the poor conductivity of the electrolyte membrane at elevated temperatures and low humidity conditions. In this context, Nanoscale Ionic Materials (NIMs) were used, placing emphasis on the study of the proton transport pathway in the presence of high ionic groups provided by the fillers surface under harsh conditions. By a new functionalization approach, NIMs anchoring high phosphonated (PO3H) and sulphonated (SO3H) ionic groups were prepared and tested as nanofillers for the creation of advanced silica-based Nafion nanocomposites through a scalable and feasible one-pot method. This approach facilitates the fine dispersion of fillers on polymer matrix, playing a synergistic effect with the sulfonic groups of Nafion in order to enhance critical properties on proton conductivity especially at drastic conditions, while the silica core improves the thermal and mechanical properties of the final composite membranes. The samples were characterized by a combination of techniques (Powder X-ray Diffraction, FTIR, Thermal Analysis and mechanical properties, impedance spectroscopy), while the Pulse Field Gradient NMR spectroscopy was used in this work to obtain a direct measurement of the water self-diffusion coefficients confined in the membranes. A remarkable behaviour at temperatures as high as 130 °C was observed for all the nanocomposite membranes, maintaining stable and unwavering diffusion for many hours at high temperatures without external humidification, proving exceptional water retention property. However, particularly interesting results were obtained on membranes containing sulphonated NIM (NIM-SO3). Membrane loaded with 1 w% of filler, shows the highest proton conductivity in all the range of temperatures and RHs investigated, reaching 0.05 S cm-1 @ 120 °C and 30% of RH. Additionally, the mechanical properties strongly increase with a shift of the polymer's α-transition of more than 50 °C. All these characteristics are highly desirable for potential use in large variety of fuel cell applications. References [1] Jespersen, M.L.; Mirau, P.A.; von Meerwall, E.; Vaia, R.A.; Rodriguez, R.; Giannelis, E.P. Advanced Materials, 2010, 20, 4353. [2] Nicotera, I.; Kosma, V.; Simari, C.; Ranieri, G.A.; Sqambetterra, M.; Panero, S; Navarra, M.A. Int. J. Hydrogen En., 2015; 40, 14651. O P 4 5 | 54 β-SUBSTITUTED PORPHYRINIC DYES WITH TUNABLE PHOTOELECTROCHEMICAL PROPERTIES Gabriele Di Carlo,*,a Alessio Orbelli Biroli,b Francesca Tessore,a Giulia Magnano,a Maddalena Pizzotti,a Stefano Caramori,c Carlo Alberto Bignozzic a Department of Chemistry, University of Milan, INSTM Research Unit, Via C. Golgi 19, 20133 Milano (Italy) b Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), Via C. Golgi 19, 20133 Milano (Italy) c Department of Chemistry and Pharmaceutical Sciences , University of Ferrara, Via Fossato di Mortara 17, 44121 Ferrara e-mail: [email protected], The facile synthesis of β-substituted porphyrins and their photoelectrochemical properties make this class of dyes very promising for application in Dye Sensitized Solar Cells (DSSCs). Although the best performances in porphyrin-sensitized solar cell has been reached by well-engineered meso disubstituted push-pull ZnII-porphyrinates, [1] these latter can be obtained only by multistep and uneconomical synthetic routes. On the contrary β-substituted ZnII-porphyrinates can easily be obtained with remarkable yields using facile synthetic procedures and they also show performances comparable or even better than the structurally corresponding meso substituted pushpull ZnII-porphyrinates.[2] This is due to a significant steric hindrance which guarantees a decrease of π-staking aggregation and a superior passivation of the TiO2 surface against charge recombination with I3-,[3] resulting highly beneficial to DSSC performances. Furthermore, the properties of porphyrinic dyes are strongly influenced by introducing various π-delocalized systems on β-pyrrolic position exerting both strong steric and electronic effects on the porphyrinic core. These induce dramatic alterations of optical, electrochemical and spectroelectrochemical properties in the porphyrinic dyes. In fact the elongation of the π-chain, in β-position, by an additional chromophore, as a dithienylethylene (DTE) unit, increases the light harvesting capacity of ZnII-porphyrinates over a wide range of wavelengths and, thus, produces a panchromatic effect in their IPCE spectra.[4] The photophysical properties of DTE meso and β-substituted ZnII-porphyrinates were comparatively investigated in order to gain insights about the excited state dynamics relevant to TiO2 sensitization of photoelectrochemical cells. Here, the results obtained by time-resolved spectroscopy, EIS investigation and DSSC performances will be discussed and compared. The information extracted from our studies should be helpful to the synthesis of novel and more efficient β-substituted porphyrinic dyes as alternatives to the more synthetically demanding meso-substituted porphyrinic counterparts. References [1] Mathew, S.; Yella, A.; Gao, P.; Humphry-Baker, R.; Curchod, B. F. E.; Ashari-Astani, N.; Tavernelli, I.; Rothlisberger, U.; Nazeeruddin, M. K. and Graetzel, M. Nat. Chem. 2014, 6, 242. [2] Di Carlo, G.; Orbelli Biroli, A.; Pizzotti, M.; Tessore, F.; Trifiletti, V.; Riffo, R.; Abbotto, A.; Amat, A.; De Angelis, F.; Mussini, P.R. Chem. Eur. J. 2013, 19, 10723. [3] Di Carlo, G.; Caramori, S.; Trifiletti, V.; Giannuzzi, R.; De Marco, L.; Pizzotti, M.; Orbelli Biroli, A.; Tessore F.; Argazzi, R.; Bignozzi, C.A. Appl. Mater. Interfaces 2014, 6, 15841. [4] Di Carlo, G.; Orbelli Biroli, A; Tessore, F.; Pizzotti, M.; Mussini, P.R.; Amat, A.; De Angelis, F.; Abbotto, A.; Trifiletti, V. and Ruffo, R. J. Phys. Chem. C 2014, 118, 7307. 55 | O P 4 6 NEW MATERIALS FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE Vito Di Noto,a,b,c,* Enrico Negro,d Keti Vezzù,d Federico Bertasi,d Giuseppe Pace,b Graeme Nawn,d Antoine Bach Delpeuch,d Gioele Pagot,a Yannick Herve Bang,d Chuanyu Sun.a a Department of Industrial Engineering, University of Padova, Via F. Marzolo 9, I-35131 Padova, Italy. CNR-IENI, Via Marzolo 1, I-35131 Padova (PD), Italy. c Consorzio Interuniversitario Nazionale per la Scienza e la Tecnologia dei Materiali, INSTM, Italy d Department of Chemical Sciences, University of Padova, Via F. Marzolo 9, I-35131 Padova, Italy. b e-mail: [email protected] For more than 25 years, the “CheMaMSE” (Chemistry of Materials for the Metamorphosis and the Storage of Energy, www.chimica.unipd.it/lab_DiNoto/) research group, led by Prof. Vito Di Noto, has been at the forefront of the research in the field of advanced nanostructured functional materials for a wide number of device families, including fuel cells (FC), electrolyzers, secondary batteries, supercapacitors, and dye-sensitized solar cells (DSSCs). The know-how of the CheMaMSE group covers the entire research spectrum for advanced energy materials from the preparation, to in-depth characterization and prototype testing. The most promising materials are adopted for the development of the next generation of energy conversion and storage devices, comprising: (i) secondary batteries; (ii) polymer electrolyte membrane fuel cells (PEMFCs); (iii) high-temperature polymer electrolyte membrane fuel cells (PEMFC); (iv) electrolysers; (v) anion-exchange membrane fuel cells (AEMFCs); (vi) redox flow batteries (RFBs); and (vii) dyesensitized solar cells (DSSCs). The complex interplay between the chemical composition, thermomechanical properties, morphology, structure and electrical response is investigated in detail by means of advanced techniques, including inductively-coupled plasma atomic emission spectroscopy (ICP-AES), high-resolution thermogravimetry (HR-TGA), modulated differential scanning calorimetry (MDSC), dynamic mechanical analysis (DMA), highresolution scanning electron microscopy (HR-SEM), high-resolution transmission electron microscopy (HR-TEM), vibrational spectroscopies (e.g., FT-IR in the medium and far infrared, confocal micro-Raman), wide-angle X-ray diffraction (WAXD), cyclic voltammetry with the thin-film rotating ring-disk electrode setup (CV-TF-RRDE) and broadband electrical spectroscopy (BES). a) b) c) Figure 1. Some examples of some materials studied by the CheMaMSE group: a) Ionic liquid based magnesium battery, b) High voltage cathode for Li- battery and c) Electrocatalyst for PEMFC, AEMFC and electrolyzers O P 4 7 | 56 GARNISHING THE PHOTOSYNTHETIC REACTION CENTER TO IMPROVE PERFORMANCES Simona la Gattaa, Francesco Milanob, Alessandra Operamollaa, Omar Hassan Omarc, Roberta Ragnia, Angela Agostianoa,b, Massimo Trottab, Gianluca M. Farinolaa a University of Bari “Aldo Moro”, Department of Chemistry, Via Orabona 4, 70126 Bari, Italy Istituto per i Processi Chimico Fisici-CNR, Department of Chemistry, Via Orabona 4, 70126 Bari, Italy c Istituto di Chimica dei Composti Organometallici-CNR, Department of Chemistry, Via Orabona 4, 70126 Bari, Italy b e-mail: [email protected] Photosynthesis is used by plants, algae and bacteria to convert solar energy into usable chemical energy. The initial stages of this process, where light is absorbed and energy and electrons are transferred, occur within the reaction center (RC) proteins, which are Nature optimized solar batteries [1]. The high photoconversion efficiency of RC, close to unit [2], is spurring efforts of the scientific community toward the construction of new materials for applications ranging from energy photoconversion to biosensing. We further demonstrate the possibility of designing organic-biological hybrid photosynthetic assemblies, for solar energy conversion by developing organicbiological hybrid systems based on the photosynthetic reaction center from the purple bacterium Rhodobacter sphaeroides strain R26 [3]. The organic counterparts is properly tailored to absorb light in the visible spectral range (400-700 nm), where the RC absorbance (Figure 1) is very low, and efficiently emit in the near infrared region (750-900 nm), in correspondence of the highest RC absorption peaks. The organic portion is not detrimental for the protein activity, is soluble in detergent aqueous environment where the RC is stable, and is endowed with a carboxylic moiety useful for their interaction with the amino groups of the RC lysine residues. Our organic-biological hybrids are capable to perform energy photoconversion like the RC and even outperform it under suitable conditions [4,5,6]. References [1] P. Maróti, M. Trotta, in CRC Handbook of Organic Photochemistry and Photobiology, CRC Press, 2012, 1289-1324. [2] C. A. Wraight, R. K. Clayton, Biochim Biophys Acta, 1974, 333, 246-260. [3] A. Operamolla, et al., J. Mater. Chem. C, 2015, 3, 6471-6478. [4] F. Milano, et al., Angew. Chem. Int. Ed., 2012, 51, 11019-11023. [5] R. Ragni, et al., G. M. Farinola, MRS Proceedings Online Library, 2014. [6] R. R. Tangorra, et al., MRS Proceedings Online Library, 2015. 57 | O P 4 8 CHEMICALLY FUNCTIONALIZED CARBON NANOTUBES WITH PYRIDINE GROUPS AS EASILY TUNABLE NDECORATED NANOMATERIALS FOR THE OXYGEN REDUCTION REACTION Giulia Tuci,a Claudio Zafferoni,b Massimo Innocenti,b Andrea Rossin,a Lapo Luconi,a Giuliano Giambastiania,* a Institute of Chemistry of OrganoMetallic Compounds, ICCOM-CNR and INSTM Consortium, 50019 Sesto F.no, Florence, Italy b Department of Chemistry, University of Florence, 50019 Sesto F.no, Florence, Italy e-mail: [email protected] Efficient and low-cost electrocatalysts capable of fostering the sluggish cathodic oxygen reduction reaction (ORR) are at the heart of renewable energy technologies based on fuel cells and other electrochemical energy devices.1 The high cost of the platinum-group metal-based electrocatalysts, together with their scarce reserves in nature, limit their sustainable commercial application in several technological energyrelated fields. Looking at effective and efficient alternatives to Pt-based electrocatalysts in ORR, N-doped carbon nanotubes have drawn much attention for their potentiality in this field. Since the first seminal report by Dai and co-workers in 2009,2 a huge effort has been made to prepare N-CNTs and exploit their catalytic properties. Among the available synthetic methods, Chemical Vapor Deposition (CVD) still remains the most widely used technique; anyway, both content (%) and type of N-doping in the final material still remain far from being easily controlled through this synthetic approach. We have recently demonstrated how a simple CNT covalent functionalization with pyridine-containing frameworks gives N-decorated nanomaterials featured by remarkable catalytic ORR performance.3 Our study offers a clear evidence of the central role played by the pyridine moieties on the electrocatalytic activity of N-CNTs in the ORR. A clear-cut evidence of the catalysts performance (in terms of process kinetics) in the ORR is provided as a function of the electronic charge density on the N-neighboring carbon atoms and the related N−Cα bond polarization.4 Overall, our alternative approach to the N-decoration of carbon nanostructures highlights the importance of the N-chemical surrounding on the ultimate catalyst performance while offering an excellent basis to the development of more catalytically active metal-free electrocatalysts for the ORR as well as an unique model for the in-depth understanding of the underlying mechanism. This work is supported by the FP7 FREECATs project (Doped carbon nanostructures as metalfree catalysts - NMP-2011-2.2-4). Authors thanks INSTM for supporting the participation of GT to Enerchem. References [1] S. Minhua, in: Electrocatalysis in Fuel Cells, A Non- and Low-Platinum Approach, Minhua, S. (Ed.), Springer, London 2013, p 327. [2] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Science 2009, 323, 760−764. [3] G. Tuci, C. Zafferoni, P. D’Ambrosio, S. Caporali, M. Ceppatelli, A. Rossin, T. Tsoufis, M. Innocenti, G. Giambastiani, ACS Catal. 2013, 3, 2108-2111. [4] G. Tuci, C. Zafferoni, A. Rossin, A. Milella, L. Luconi, M. Innocenti, L. Truong Phuoc, C. Duong-Viet, C. Pham-Huu, G. Giambastiani, Chem. Mater. 2014, 26, 3460-3470. O P 4 9 | 58 HYBRID SYSTEMS BASED ON CDSE NANOCRYSTALS IN LOW BAND GAP COPOLYMER FOR SOLAR CELLS A. E. Di Mauro,a S. Zappia,b R. Mastria,c,d A. Rizzo,d S. Destri,b M. L. Curri,a R. Tommasi,e A. Agostiano,f,a M. Striccoli*,a a CNR-IPCF-Bari Division, c/o Chemistry Department, University of Bari Aldo Moro, Via Orabona 4, 70126 Bari, Italy. b CNR-Istituto per lo Studio delle Macromolecole, Via E. Bassini 15, 20133, Milano, Italy. c Dipartimento di Matematica e Fisica ‘E. De Giorgi’, Università del Salento, via per Arnesano, 73100, Lecce, Italy. d CNR NANOTEC - Istituto di Nanotecnologia, Polo di Nanotecnologia c/o Campus Ecotekne, via Monteroni, 73100, Lecce, Italy. e Department of Basic Medical Sciences, Neurosciences and Sense Organs, University of Bari Aldo Moro, P.zza G. Cesare 11, 70124 Bari, Italy. f Chemistry Department, University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy. e-mail: [email protected] Colloidal nanocrystals (NCs) based hybrid solar cells (HSCs) have received significant interest as an alternative to all-organic solar cells, thanks to the solution-processability and the high mechanical flexibility of organic component, and to the high charge mobility and the tunable optoelectronic properties of the inorganic counterpart [1]. In particular, CdSe NCs are widely studied and successfully used for the preparation of bulk heterojunction solar cells in conjunction with conjugated polymers [2]. Here, CdSe NCs have been combined with a low band gap copolymer, poly[2,6-(4,4-bis-(2ethylhexyl)-4H-cyclopenta[2,1-b;3,4-bʹ]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) to be used as active layer in a hybrid photovoltaic device. First, ultrafast transient absorption spectroscopy has been used to probe, in visible and NIR spectral regions, energy transfer, electronic interactions and photo-generation of charges at the interface between NCs and conjugated polymer in blends deposited in thin film. Then, a rod-coil block copolymer (BC), namely polycyclopentadithiophene-benzothiadiazoleblock-poly(4-vinylpyridine) (PCPDTBT-b-P4VP) has been purposely designed and synthesized to be used as nanostructuring compatibilizer in CdSe NCs/PCPDTBT blend. In fact, the control of the active layer morphology is a key factor to improve photovoltaic performance as, ideally, an interpenetrating network of the polymer and the NC domains is crucial to maximize charge separation, transfer and transport. The employment of the rod-coil BC as additive is demonstrated to be an effective alternative to the standard post-deposition thermal treatment: the fabricated device with 1% of additive shows an improvement of 55% in power conversion efficiency (PCE 1.16%) if compared to CdSe NCs/PCPDTBT based solar cell. The optical and morphological analysis of the CdSe NCs/PCPDTBT films elucidates the relation between the device performance and the active layer microstructure. References [1] Reiss, P.; Couderc, E.; De Girolamo, J.; Pron, A. Nanoscale 2011, 3, 446. [2] Greaney, M. J.; Brutchey, R. L. Mater. Today 2015, 18, 31. 59 | O P 5 0 SYNERGISTICALLY ENHANCED PERFORMANCES OF Pt NANOPARTICLES ON DOPED MESOPOROUS CARBON FOR OXYGEN REDUCTION REACTION Durante C., Perazzolo V., Picelli L., Rizzi G.A., Granozzi G., Gennaro A. Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova e-mail: [email protected] Mesoporous carbons (MCs) are highly porous materials, which offer high surface area, chemical inertness and superior electrochemical performance with respect to traditional carbon materials [1]. Hetero-functional groups introduced into a carbon support appear to influence at least three aspects of the catalyst/support system: i) affect the nucleation and growth kinetics during catalyst nanoparticle deposition, ii) increase the support/catalyst chemical binding, which results in enhanced durability and iii) modify catalyst nanoparticle electronic structure, which enhances intrinsic catalytic activity [2]. In this work, nitrogen- or sulphur-doped (N-MC and S-MC) and dual doped MC (S,NMC) are modified with Pt nanoparticles (Pt@N-MC, Pt@S-MC and Pt@N,S-MC) in order to verify the presence of these three distinct effects. The Pt loading was set to 25% (wt.) in order to compare the catalytic activity with commercial standards of high Pt content. Several Pt salt precursors and deposition conditions were tested in order to obtain the best particle dispersion and dimension. It is found that Pt deposition from Pt(acac)2 affords the best results in terms of NPs dimension and dispersion. TEM analysis suggests the formation of very small NPs (1-3 nm) well dispersed inside and outside the mesopore structure of the carbon support (Fig. 1a), whereas XPS proved a slightly interaction between Pt and nitrogen and/or sulfur [3] Linear sweep voltammetry was used to characterize electrocatalytic activity of the synthetized materials, and to compare their performances with respect to commercial Pt-supported undoped Vulcan (Tanaka, Pt loading 50 %). All synthetized Pt cathodes exhibit excellent electrocatalytic activity, which is comparable to or even higher than that of the standard material with higher Pt content. Electrochemical stability tests were also be carried out to elucidate the degradation of Pt nanoparticles. a b Figure 1: (a) TEM image of Pt@N-MC, (b) RDE LSV in O2-saturated 0.5 M H2SO4. We acknowledge financial support from Joint Undertaking (FCH-JU) within the CathCat project under contract No. 303492 References [1] V. Perazzolo, C. Durante, R. Pilot, A. Paduano, J. Zheng, G.A. Rizzi, et al., Carbon 95 (2015) [2] A.S. Bandarenka, M.T.M. Koper, J. Catal. 308 (2013) 11–24. [3] L. Perini, C. Durante, M. Favaro, V. Perazzolo, S. Agnoli, O. Schneider, et al., ACS Appl. Mater. Interfaces. 7 (2015) 1170–1179. O P 5 1 | 60 XPS SURFACE CHARACTERIZATION OF ELECTROCHEMICALLY DEPOSITED SEMICONDUCTORS FOR PHOTOVOLTAIC APPLICATIONS Rosaria Anna Picca*,a Serena Cinotti,b Andrea Giaccherini,b Maria Chiara Sportelli,a Francesco Di Benedetto,c Massimo Innocenti,b Nicola Cioffia a Chemistry Department, University of Bari “Aldo Moro”, Via. E. Orabona 4, Bari, Italy Chemistry Department, University of Firenze, Via della Lastruccia 3, Sesto Fiorentino (FI), Italy c Earth Sciences Department, University of Firenze, Via G. La Pira 4, Firenze, Italy b e-mail: [email protected] The development of solar cells based on inorganic thin films represents a continuously expanding research field. Researchers are constantly involved in the study of low-cost, eco-compatible, and efficient materials to go beyond Silicon for photovoltaic applications [1]. In particular, possible scaling-up of device production cannot proceed via the use of rare (In, Ga, Te) or toxic (Cd) elements [2,3]. Ternary (e.g. CuxSnySz) and quaternary (e.g. kesterite,Cu2ZnSnS4 or CZTS) chalcogenide-like materials may be prepared according to different methodologies [4–6]. A valid approach, thoroughly investigated in Florence laboratories [2,7], is the Electrochemical Atomic Layer Deposition (E-ALD) [8] for the growth of multinary sulfide thin films on conducting substrates (e.g. Ag(111)). In a complete E-ALD cycle, monolayers of different composition are obtained by alternating the underpotential deposition of the metallic element with the underpotential deposition of the non-metallic element. The number of cycles, as well as other parameters (e.g. composition of the deposition bath, applied potential, etc.) influence the composition and properties of the resulting material. X-ray Photoelectron Spectroscopy (XPS) can be applied to assess the surface chemical composition of the electrodeposited thin films [6,7]. In this communication, we present our recent results on the XPS characterization of different multinary systems, showing how this spectroscopic technique can help discriminating different chemical environments. These findings can be correlated to results obtained with other morphological (Scanning Electron Microscopy) and spectroscopic techniques (e.g. in situ Surface X Ray Diffractometry with Synchrotron Radiation). Moreover, angleresolved XPS mode provided detailed information on in-depth element distribution. References [1] Miles, R. W.; Zoppi, G.; Forbes, I. Mater. Today 2007, 10 (11), 20–27. [2] Di Benedetto, F.; Bencistà, I.; Caporali, S.; Cinotti, S.; De Luca, A.; Lavacchi, A.; Vizza, F.; Muniz Miranda, M.; Foresti, M. L.; Innocenti, M. Prog. Photovolt. Res. Appl. 2014, 22 (1), 97–106. [3] Todorov, T. K.; Tang, J.; Bag, S.; Gunawan, O.; Gokmen, T.; Zhu, Y.; Mitzi, D. B. Adv. Energy Mater. 2013, 3 (1), 34–38. [4] Jimbo, K.; Kimura, R.; Kamimura, T.; Yamada, S.; Maw, W. S.; Araki, H.; Oishi, K.; Katagiri, H. Thin Solid Films 2007, 515 (15), 5997–5999. [5] Guo, Q.; Hillhouse, H. W.; Agrawal, R. J. Am. Chem. Soc. 2009, 131 (33), 11672–11673. [6] Gordillo, G.; Calderón, C.; Bartolo-Pérez, P. Appl. Surf. Sci. 2014, 305, 506–514. [7] Caporali, S.; Tolstogouzov, A.; Teodoro, O. M. N. D.; Innocenti, M.; Di Benedetto, F.; Cinotti, S.; Picca, R. A.; Sportelli, M. C.; Cioffi, N. Sol. Energy Mater. Sol. Cells 2015, 138 (0), 9–16. [8] Gregory, B. W.; Stickney, J. L. J. Electroanal. Chem. Interfacial Electrochem. 1991, 300 (1–2), 543–561. 61 | OP52 TAILORING MATERIALS PROPERTIES THROUGH DEFECTS AND STRAIN: THE EXAMPLE OF PEROVSKITE-TYPE LaGaO3 Cristina Tealdi,a Piercarlo Mustarellia a Department of Chemistry, University of Pavia and INSTM, Viale Taramelli 16, 27100 Pavia, Italy e-mail: [email protected] Lattice strain is a promising possibility to improve materials performance in view of their application in thin-film devices. In particular, defect and transport properties in ionic conductors may be tailored through strain effects, since defect formation energy and migration barriers are correlated to structural parameters which, in turn, are influenced by strain-induced deformations. A major and highly debated example in this field is the extraordinary increase in conductivity in ultrathin YSZ films (Y2O3-doped ZrO2).1 Recent computational results on fluorite-structured oxides also point towards a relevant effect of strain on the transport properties of fluorite-type oxides.2-5 These results, if confirmed, would be of paramount relevance for many technological applications, including Solid Oxide Fuel Cells (SOFCs). A material of choice as electrolyte for intermediate temperature SOFCs is perovskitetype LaGaO3. This material provides its better performances in terms of ionic conductivity when doped with Sr and Mg on the La and Ga sites, respectively.6 The perovskite structure, with its rich variety of structural distortions due to octahedral tilting, offers a great possibility to investigate how strain and defects influence structural and in turn transport properties. Moreover, LaGaO3 represents an example of the large family of perovskites-structured functional oxides finding application in different technological fields (e.g. superconductors, ferroelectrics, catalysts, …), where both device engineering and performances require that these materials be present in the form of thin films. In this computational study,7 we investigated by means of atomistic simulation techniques (both energy minimization and molecular dynamics) the effect of biaxial strain on the transport properties of lanthanum gallate, with emphasis on dopant-vacancy association effects. We predicted that oxide-ion diffusion in perovskite-type lanthanum gallate can be considerably improved through the application of tensile strain. The structural deformations required to accommodate tensile lattice strain in the perovskite system are shown to result in a preferential localization of the oxygen vacancies in the equatorial plane of the GaO6 octahedra, while oxide-ion diffusion becomes anisotropic along with strain. References [1] J. Garcia-Barriocanal et al., Science 2008, 321, 676. [2] A. Kushima et al, J. Mater. Chem. 2010, 20, 4809. [3] R. A. De Souza et al., Energy Environ. Sci. 2012, 5, 5445. [4] G. Dezanneau et al, Int. J. Hydrogen Energy 2012, 37, 8081. [5] M.J.D. Rushton et al., Solid State Ionics 2013, 230, 37. [6] T. Ishihara et al., J. Am. Chem. Soc. 1994, 116, 3801. [7] C. Tealdi et al., J. Phys. Chem. C 2014, 118, 29574. O P 5 3 | 62 ALTERNATIVE BUFFER LAYERS DEPOSITED BY RADIO FREQUENCY SPUTTERING FOR CHALCOGENIDE THIN FILMS SOLAR CELLS R. A. Mereu,a M. Acciarri,a A. Le Donne,a M. Boshta,b S. Binetti,a* a University of Milano Bicocca, Dept. of Materials Science and Solar Energy Research Center (MIBSOLAR), Via R. Cozzi 55, 20125 Milan, Italy b National Research Centre, El-behooth 12311,Dokki,Giza, Egitto e-mail: [email protected] Thin film solar cells based on Cu(In,Ga)Se2 (CIGS) yield up to now, a maximum photovoltaic conversion efficiency of 21.7% if CdS deposited by chemical bath deposition is used as buffer layer. However, due to the disadvantages of CdS (like the toxicity classification of Cd, the non-vacuum nature of the chemical bath deposition and the absorption of blue light) an extensive research was employed in the last years on finding new alternative buffer layers. Thereby, in this work different alternative materials like, Zn2SnO4, In2S3 and ZnS are investigated as alternative buffer layers for CIGS solar devices by using radio frequency sputtering method in the view of an roll to roll vacuum deposition. Apart from the basic optical, structural and morphological properties of the individual single layers our research was focused on the optimization of the deposition process for each layer. Thereby, a special attention was assigned to the influence of the deposition parameters like thickness, pressure and frequency, respectively. Furthermore, different CIGS and CZTS (Cu2ZnSnS4) solar devices were prepared with Zn2SnO4, In2S3 and ZnS buffer layers and CdS as reference, and completed with standard front contact (i-ZnO and AZO). The solar devices thus obtained were investigated by means of current voltage (J-V) characteristics and the external quantum efficiency (EQE) was measured to investigate the photogeneration of carriers and any possible collection loss. Since the alternative buffer layer tested up to now have resulted in efficiency values lower than those obtained with the CdS buffer layer further optimizations are currently in progress. Acknowledgments This work was partially supported by the European Commission through the project SolarDesign (contract no. FP7-NMP-2012-SME-6) and by the executive programme of scientific and technological cooperation between Italy and Egypt through the Joint Research Project PGR00116. 63 | OP54 CATHODE CATALYSTS DEVELOPMENT FOR POLYMER ELECTROLYTE FUEL CELLS Vincenzo Baglio,* David Sebastián, Alessandro Stassi, Sabrina C. Zignani, Ada Saccà, Irene Gatto, Antonino S. Aricò CNR-ITAE, Via Salita S. Lucia sopra Contesse 5 – 98126 Messina, Italy e-mail: [email protected] Advances in fuel cell technology demand a reduction of costs, a decrease of Pt loading and optimization of catalyst utilization [1]. In addition, for an easy thermal and water management, the automotive fuel cell market requires an increase of the working temperature almost up to 130 °C and operation with low relative humidity (R.H.), less than 50% [2]. This could favor the large diffusion of polymer electrolyte fuel cells (PEFCs). In the last few years, the research on electrocatalysts has been mainly focused on the enhancement of intrinsic activity for the oxygen reduction reaction (ORR). A successful approach to enhance the electrocatalysis of O2 reduction is by alloying Pt with transition metals [3]. These alloys lead to an increase of the mass activity with respect to the conventional Pt/C catalyst and consequently to a decrease of the platinum content. Despite the interesting performances obtained by using such catalysts, an improvement of the ORR kinetic is still necessary at intermediate temperatures (100– 130 °C) and under low R.H. (50% or less). In the present work, carbon supported Pt-Co and Pt-Ni catalysts have been prepared and characterized in terms of bulk and surface composition, structure and morphology. They have been investigated in PEFCs under automotive conditions (high temperature and low R.H.) and compared to a benchmark Pt/C catalyst. Acknowledgement. The research leading to these results has received funding from the European Union’s Seventh Framework Programme (FP7/2007-2013) for Fuel Cell and Hydrogen Joint Technology Initiative under Grant no 303452 (IMPACT). References [1] Gasteiger, H.A.; Kocha, S.S.; Sompalli, B.; Wagner, F.T. Appl. Catal. B: Environ. 2005, 56, 9. [2] Stassi, A.; Gatto, I.; Baglio, V.; Aricò, A.S. Int. J. Hydrogen Energy 2014, 39, 21581. [3] Chen, S.; Sheng, W.; Yabuuchi, N.; Ferreira, P.J.; Allard, L.F.; Yang, S.H. J. Phys. Chem. C. 2009, 113, 1109. P 0 1 | 64 MESOPOROUS SILICA-BASED NAFION COMPOSITES MEMBRANES FOR APPLICATIONS IN SINGLE-CHAMBER MICROBIAL FUEL CELLS (MFC) Luca Millia,a Simone Angioni,a Gianna Bruni,a Piercarlo Mustarelli,a Eliana Quartarone*,a a Department of chemistry, University of Pavia, Via Taramelli 12, Pavia, Italy. e-mail: [email protected] Today the wastewater treatment processes are still energetically intensive, expensive and require high investments. Microbial fuel cells (MFC) are appealing bioreactors for the simultaneous electricity generation and wastewater treatment. In the particular field of the single-chamber MFC, several membranes have been tested during these last years. Among them, proton conductive membranes, which separate the anodic compartment from the cathodic one, have a high impact on power density. Nafion 117 is a typically investigated proton exchange membrane (PEM) for MFC applications, even if some questions are still open, a high cost, bacteria biofouling and oxygen crossover. Here, we describe different Nafion composite membranes based on mesoporous silica, pristine and properly functionalized with sulfonic acid units, in order to investigate the role of the filler in the improvement of the MFC functional performances. These systems were compared with cells including pure Nafion 117 membranes. The microbial fuel cells were assembled sandwiching the membranes among carbon clothes as anode and Pt-loaded GDL as cathode and analysed in municipal wastewater environment. The bioreactors were characterized in terms of electrochemical impedance spectroscopy, polarization experiments, COD determination and SEM analyses on the electrode compartments before and after the test. After 2000 hours of continuous work, the MFCs provide power densities, ranging between 96 and 282 mW/m3 depending on the composite membrane. At the same time, decreases of the MFC interfacial resistance were also observed switching from the pure Nafion membranes to the composite ones. In particular, the best results were obtained with the cell containing the Nafion composites filled with the sulfonated mesoporous silica that delivered a constant power density higher than about 300 mW/m3. In such cases, SEM analysis showed a negligible biofouling contrary to the pure Nafion membranes, where a highly packed film made of rod-shaped microorganisms, arranged in long chains, were detected. 65 | P02 SOLID STATE NMR ANALYSIS OF SOLAR CELL MATERIALS Roberto Avolio,a Antonio Abate,b Maria Emanuela Erricoa a Institute for Polymers, Composites and Biomaterials (IPCB-CNR), via Campi Flegrei 34, 80078 Pozzuoli, Italy. b Adolphe Mercke Institute, University of Fribourg, Chemin des Verdiers 4, CH-1700 Fribourg, Switzerland. e-mail: [email protected] Photovoltaic (PV) cell technology has been experiencing a continuous development during last years, with new device architectures and improved performance claims being published at a very fast rate [1]. Recently the emergence of halide perovskitebased solar cells represents one of the lowest cost technologies, capable of the highest sunlight conversion efficiencies [2]. Solid state (SS) NMR is a powerful technique that can be applied to a broad range of compounds, providing information on molecular structure and mobility. It is particularly suited for the analysis of multiphase, hybrid organic/inorganic structures as it can probe different nuclei (allowing to observe both the organic and the inorganic phases) and can provide a molecular-level focus on the interfacial phenomena that plays a key role in the definition of final properties. SS NMR was employed to clarify the role of lithium in increasing the conductivity of the hole-transport layer (Spiro-OMETAD) in ss-DSSCs [3]. An active redox behavior of Li-TFSI salt was observed that lead to a doping of the hole transporter, involving also oxygen absorbed from the atmosphere. The formation of lithium oxide species was suggested by 7Li NMR recorded on the Spiro – LiTFSI system after exposure to oxygen. 19 F and 13C NMR experiments were used to investigate the coordination of iodopentafluorobenzene (IPFB) on halide-lead perovskite crystals [4]. The IPFB treatment of perovskite based devices led to a clear improvement of the efficiency that was ascribed to the passivation of the uncoordinated halide anions at the surface. The shift observed in NMR spectra proved the formation of a halogen bond between the iodine of IPFB and the surface ions of perovskite. References [1] Yu, J.; Zheng, Y.; Huang J. Polymers 2014, 6, 2473. [2] Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. [3] Abate, A.; Leijtens, T.; Pathak, S.; Teuscher, J.; Avolio, R.; Errico, M.E.; Kirkpatrik, J.; Ball, J.M.; Docampo, P.; McPherson, I.; Snaith, H.J. Phys. Chem. Chem. Phys. 2013, 15, 2572. [4] Abate, A.; Saliba, M.; Hollman, D.J.; Stranks, S.D.; Wojciechowski, K.; Avolio, R.; Grancini, G.; Petrozza, A.; Snaith H.J. Nano Letters 2014, 14, 3247. P03 | 66 ELECTROCHEMISTRY OF THIOPHENE CONTAINING ORGANIC SENSITIZERS FOR DYE-SENSITIZED SOLAR CELLS Clara Baldoli,a Lucia Viglianti,b Alessandro Bolzoni,b Alberto Bossi,a Patrizia Romana Mussini,b Emanuela Licandrob a CNR - Istituto di Scienze e Tecnologie Molecolari (ISTM) and SmartMatLab Center. Via C. Golgi 19. 20133 Milano (Italy) b Dipartimento di Chimica - Università degli Studi di Milano. Via C. Golgi 19. 20133 Milano (Italy) e-mail: [email protected]; [email protected] We synthesized a series of new push-pull metal-free dyes in which the donor and the acceptor fragments are the classical triarylamino and cyanoacrylic groups, and the πspacer is constituted by benzo[1,2-b:4,3-b’]dithiophene, (BDT), benzo[1,2-b:4,5b’]dithiophene, (BDT1) and tetrakis(2-thienyl)ethene (TTE). The novel chromophore series have been the object of a detailed molecular electrochemistry study. We have determined HOMO-LUMO gaps and the electron transfer properties of the electron rich and electron poor terminal redox sites, as a function of the conjugation efficiency, of the substituent effects and of the π -spacer system. The electrochemical results have been compared with spectroscopic data. S S S S S S S BDT S BDT1 TTE References [1] Li, D.; Yuan, Y.; Bi, H.; Yao, D.; Zhao, X.; Tian, W.; Wang, Y.; Zhang, H. Inorg. Chem. 2011, 50, 4825. 67 | P04 POLYMETHINE DYES AS NIR SENSITIZERS FOR DSCs Nadia Barbero,* Simone Galliano, Davide Saccone, Claudia Barolo, Pierluigi Quagliotto, Guido Viscardi University of Torino, Department of Chemistry and NIS Interdepartmental Centre, Via P. Giuria 7, Torino, 10125, Italy. e-mail: [email protected] NIR conversion is indubitably interesting in order to widen solar harvesting and tune the colours of final devices. Being the component responsible for the solar light harvesting, the photosensitizer has a crucial role in a DSC system. In order to accomplish this function, some requirements are needed: i) a panchromatic absorption (400 – 920 nm); ii) high molar extinction coefficient; iii) appropriate matching with the energy levels of the semiconductor and the redox mediator; iv) a stable grafting on the semiconductor surface; v) high chemical and photo-chemical stability; vi) easy and tunable synthesis with a high efficiency/cost ratio. Different classes of sensitizers have been proposed so far: organo-metallic, organic and inorganic molecules.[1] However it is difficult to find a sensitizer fulfilling all the above-mentioned requirements. Polymethine dyes (i.e. cyanines as well as squaraines) are well known for their far-red NIR absorption with very high molar extinction coefficients, intense and sharp absorption bands, interesting optical properties and considerable photostability.[2] Moreover, it is possible to tune their design and synthesis to widen the absorption in the far red and near infrared domain. We have developed a few series of new efficient organic sensitizers based on squaraine core-units,[3] cyanines and croconines with a shifted absorption as high as 830 nm. We present here these new efficient sensitizers converting up to 20% IPCE until 950 nm: their synthesis as well as their light-to-electricity performances which have been optimized by using highly diluted dye solution to promote aggregate-free selfassembled monolayer and carefully chosen electrolyte composition. References [1] Barbero, N.; Sauvage, F. in Materials for Sustainable Energy Applications: Conversion, Storage, Transmission and Consumption (Eds.: X. Moya, D. Munoz-Rojas), CRC Press, 2016, pp. 87–147. [2] Park, J.; Viscardi, G.; Barolo, C.; Barbero, N. Chimia. 2013, 67, 129–35. [3] Barbero, N.; Magistris, C.; Park, J.; Saccone, D.; Quagliotto, P.; Buscaino, R.; Medana, C.; Barolo, C.; Viscardi, G. Org. Lett. 2015, 17, 3306–3309. P05 | 68 NOVEL NON-AQUEOUS AMINE SOLVENTS FOR BIOGAS UPGRADING Francesco Barzagli,a Fabrizio Mani,a Maurizio Peruzzinia a Institute of Organometallic Chemistry (ICCOM), National Research Council (CNR), via Madonna del Piano 10, 50019 SestoFiorentino, Florence, Italy e-mail: [email protected] Reducing the CO2 and H2S contents of biogas is a prerequisite to raise its quality to that of natural gas. The chemical capture of carbon dioxide was accomplished with nonaqueous single 2-amino-2-methyl-1-propanol (AMP), 2-(tertbutylamino)ethanol (TBMEA), 2-(isopropylamino)ethanol (IPMEA), and N-methyl-2,2′-iminodiethanol (MDEA), with their 1:1 blends dissolved in either an ethylene glycol/1-propanol mixture or single diethylene glycol monomethyl ether. The gas mixtures used contain either 15 or 40% CO2 in air, sometimes added with 50 ppm H2S. We designed two different experimental procedures: (1) separate experiments of CO2 absorption and desorption aimed at selecting the most efficient amines and (2) continuous cycles of CO2 absorption (20 °C) and desorption (90−95 °C) featuring CO2 removal efficiency in the range of 89−96%. The CO2/amine/alcohol equilibria were analyzed by 13C nuclear magnetic resonance (NMR) spectroscopy, which allowed us to identify and quantify the carbonated species in solution originated from both amine and alcohol carbonatation. In some continuous cycles of CO2 absorption, H2S was selectively captured by aqueous H2O2 and separated as either elemental sulfur or CaSO4. 69 | P06 CARBON DIOXIDE UPTAKE AS AMMONIA AND AMINE CARBAMATES AND THEIR EFFICIENT CONVERSION INTO UREA AND 1,3-DISUBSTITUTED UREAS Francesco Barzagli,a Fabrizio Mani,a Maurizio Peruzzinia a Institute of Organometallic Chemistry (ICCOM), National Research Council (CNR), via Madonna del Piano 10, 50019 SestoFiorentino, Florence, Italy e-mail: [email protected] Solid mixtures of ammonium carbamate and bicarbonate originating from the CO2 capture by NH3 in water-ethanol solution were converted into urea by heating to 165 °C for 60-90 min. The yield of urea was up to 53% on molar basis. An analogous technique was employed to capture CO2 with 1-aminobutane, 1-amino-2methylpropane, 2-amino-2-methylpropane, 1-aminooctane, aminocyclohexane and 1,4diazacyclohexane, in organic solvents as amine carbamates which were separated in the solid state and thermally converted at 150 °C for 15-16 h into 1,3-disubstituted ureas with 30-40 % yield on molar scale. The formation of 1,3-disubstituted ureas was 100% selective. The rate of the conversion reaction was significantly improved in the presence of copper catalysts. The identification and quantification of the products in the reaction mixtures were obtained by 13C NMR analysis. P07 | 70 HYPER FLEXIBLE DYE-SENSITIZED SOLAR CELLS: TOWARDS MICROFLUIDIC STABLE DEVICES Federico Bella,*,a Andrea Lamberti,b Stefano Bianco,b Elena Tresso,b Candido Fabrizio Pirri,b Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 – Torino, Italy. b MPMNT Group, Department of Applied Science and Technology - DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 – Torino, Italy. e-mail: [email protected] One of the possible applications of dye-sensitized solar cells (DSSCs) is the biasing of low-power portable devices. However some critical issues still have to be faced in view of obtaining flexible cells, readily adaptable to complex shapes. Until today the best performing DSSCs are based on a rigid housing with glass/FTO electrodes and the use of a liquid electrolyte is crytical for the possible durability of the device. Therefore, suitable flexible electrodes and polymeric electrolytes are needed. During recent years we deepened a promising approach for the fabrication of quasisolid DSSCs with excellent long-term durability. We thoroughly studied and characterized the integration of self standing polymeric membranes prepared by free radical photopolymerization, investigating different polymeric formulations. Very recently, this electrolytic system was integrated with an innovative design for DSSC photoanode, based on the use of semitransparent metallic meshes as a support for the sensitized nanostructured semiconductor [1]. For photoanode fabrication, both the use of TiO2 nanotubes directly grown on bendable Ti mesh by anodic oxidation and the deposition of mesoporous layers of TiO2 nanoparticles were investigated with excellent results. The main advantage of this solution is the possibility to perform the high temperature sintering process (which is mandatory for a well performing semiconductor layer with good electron transport) before the integration on the final polymeric housing. In this work, two flexible electrodes (a titanium mesh supporting N719-sensitized TiO2 nanotubes by anodic oxidation and a Pt-coated mesh) are embedded in flexible PDMS substrates obtained by partial crosslink reaction before bonding. PDMS is almost totally transparent to VIS radiation down to 220 nm, thus it represents a valuable substrate for flexible DSSCs. Moreover, the two PDMS substrates can be sealed by means of UV-cured siloxane methacrylates, thus avoiding the use of thermoplastic films that would require pressure and high temperatures. Furthermore, PDMS is well suited for the fabrication of microfluidic devices [2], so it is possible to create holes and channels for the introduction of liquid electrolytes or UV-curable monomers containing different redox couples. The photovoltaic behavior of the resulting solid DSSCs is exhaustively investigated by electrical measurements and impedance spectroscopy. References [1] Bella, F.; Lamberti, A.; Sacco, A.; Bianco, S.; Chiodoni, A.; Bongiovanni, R. J. Membr. Sci. 2014, 470, 125. [2] Lamberti, A.; Virga, A.; Angelici, A.; Ricci, A; Descrovi, E.; Cocuzza, M.; Giorgis, F. RSC Adv. 2015, 5, 4404. 71 | P08 ENERGY AND CHEMICALS FROM THE SELECTIVE ELECTROOXIDATION OF RENEWABLE DIOLS BY ORGANOMETALLIC FUEL CELLS (OMFCs) Marco Bellini *a, Maria Gelsomina Folliero a,b, Maria Vincenza Pagliaro a, Hamish Artur Miller a, Jonathan Filippi a, Alessandro Lavacchi a, Andrea Marchionni a, Werner Oberhauser, a Francesco Vizza a a Institute of Chemistry of the Organometallic Compounds – National Research Council, Via Madonna del Piano 10, 50019 Sesto Fiorentino (Florence), Italy. b Department of Biotechnology, Chemistry and Pharmacy, Via Aldo Moro 2, 53100 Siena, Italy. e-mail: [email protected]. Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol to their corresponding mono-carboxylates [1]. Model reactions in homogeneous solution were performed to rationalize the electrocatalytic cycles [1,2]. On the electrode surface, the precursor 1@C is rapidly converted into the hydroxo complex, [Rh(OH)(trop2NH)(PPh3)]@C (2@C), which is in a rapid equilibrium with the amide [Rh(trop2N)(PPh3)]@C (3@C) and water. The amide 3@C dehydrogenates diols to aldehydes. Under the basic reaction conditions, the aldehydes are rapidly further converted promoted by catalyst 2@C to form carboxylate ions and 5@C. The latter complex is oxidized at the electrode, releasing two H+ (neutralized to give water under basic conditions) and two electrons with regeneration of the amide 3@C. (Scheme 1) [1,2]. We believe that a wide range of possible combinations of organometallic complexes and conducting support materials can be applied to produce, under waste-free conditions, chemicals which may be of industrial relevance [1]. Scheme 1: Supposed catalytic cycle for alcohols oxidation in OMFCs. References [1] Bellini, M.; Bevilacqua, M.; Filippi, J.; Lavacchi, A.; Marchionni, A.; Miller, H.A.; Oberhauser, W.; Vizza, F.; Annen, S.P.; Grützmacher, H.; ChemSusChem. 2014, 7, 2432. [2] Annen, S.P.; Bambagioni, V.; Bevilacqua, M.; Filippi, J.; Marchionni, A.; Oberhauser, W.; Schönberg H., Vizza, F.; Bianchini, C.; Grützmacher, H.; Angwe.Chemie-Int. Ed. 2010, 49, 7229. P09 | 72 ELECTROCHEMICAL ATOMIC LAYER DEPOSITION OF P & N SEMICONDUCTOR FILMS FOR PHOTOVOLTAIC APPLICATIONS Enrico Berrettia, Francesco Di Benedettoc, Nicola Cioffib, Ferdinando Capolupoa, Alessandro Lavacchid, Rosaria Anna Piccab, Andrea Comparinia, Maurizio Passapontia, Massimo Innocentia. a Chemistry Department, University of Firenze, Florence, Italy. Chemistry Department, University of Bari “Aldo Moro”, Bari, Italy. c Department of Earth Sciences, University of Firenze, Florence, Italy d Institute of Chemistry of Organometallic Compounds, CNR, Florence, Italy b mail: [email protected] In the search of a viable alternative to silicon wafer-based cells, thin film solar cells are the ones that show better performances, such as higher durability and conversion efficiency. Their main drawback resides in the production process, which is today limited by the need of rare and expensive elements (the common thin film cells use CdTe or Cu(In,Ga)Se2), as well by the employment of difficult and energy expensive processes for their fabrication. Therefore research in the photovoltaic field needs to focus on alternatives to minimize the exploitation of these rare elements and on more sustainable production processes. Compounds such as Kesterites (CZTS, ternary and quaternary copper and zinc sulfides) could be used in virtue of their semiconductor behavior; also, to simplify the productive process, electrodeposition from acqueous media was proposed; in particular E-ALD (Electrochemical Atomic Layer Deposition) method seems a legit alternative to the high pressure and temperature methods used since today. My work focused on the preparation of two layers of semiconductors, one above the other, to assess the possible usage of the obtained film in the photovoltaic field; first a CuZnS (Kesterite precursor with p electronic proprieties) layer was obtained on an Ag(111) substrate, then the other binary CdS (with n electronic proprieties) layer was grown over. These single compounds and their deposition by means of E-ALD method were largely studied by my research group, but their union to form a junction wasn't tested already. Therefore the first step of my work was the study of the deposition conditions of the CdS on the CuZnS. Using cyclic voltammetry i was able to detect at first the electrochemical inactivity window of the ternary compound, and then the deposition potentials of the Cd and S on the ternary. To determine if the binary compound shows the underpotential deposition phenomenon above the ternary compound, two deposition methods were tested. The first uses the EALD methodology, the second was a simple charge-controlled deposition method. The obtained samples were characterized morphologically, qualitatively and optically. Scanning electron mycroscopy (SEM) was used to evaluate both the morphological and the compositional aspects. Composition was also evaluated by x-ray photoelectronic spectroscopy (XPS). In the end diffused reflectance UV-vis spectrometry (DRS) was used to determine the photoadsorbance of the samples. 73 | P10 ELECTRODEPOSITION OF ALUMINIUM FOR GAS TURBINE APPLICATIONS: INFLUENCE OF THE BOND COAT DEPOSITION PARAMETERS ON THE CORROSION RESISTANCE Enrico Berrettia, Andrea Giaccherinia, Stefano Martinuzzia, Stefano Caporali,b Massimo Innocentia a b Chemistry Department, University of Florence, Florence, Italy. INSTM, Florence, Italy. e-mail: [email protected], Gas turbines are widely used for energy production. One of the critical points limiting turbines service life and performances is represented by hot corrosion resistance of their blades. Nowadays most of the research effort aims to improve blades performances, it is focuses in the development of better thermal barrier coatings (TBC) and bond coats (BC), in order to obtain higher working temperatures, better efficiencies and longer work life. The bond coat layer in particular, acting as a intermediate layer between the substrate and the TBC, is the most prone to thermal stress and corrosion; is commonly made by aluminium (and its alloys) deposited on the substrate by PVD or pack cementation. These deposition methods are costly, energy consuming and doesn’t allow the obtainment thick aluminum layers. On the contrary, electrodeposition of aluminium from ionic liquids (ILs) could lead to a less energy consuming process, and to thicker deposits. In fact, since their discovery, ILs have attracted a wide interest for their potential use as electrolytes, allowing the electrodeposition of metals that are impossible to reduce in aqueous media. In particular chloroaluminated ILs have made possible the deposition of Aluminium from his chloride salt. Despite the discovery of this process in the nineties, nowadays aluminium electrodeposition from chloroaluminate ILs still maintains a number of open issues both on the side of fundamental science and technological aspects. The present communication aims both to assess the feasibility of the electrodeposition of aluminium from ionic liquids for an industrial application, and to shed some light on the aluminium electrodeposition process as concern the effect of deposition parameters. Thick Al-coatings (20 µm) were deposited on brass substrates at different temperature, potential and mixing conditions. Then, the coatings morphology and phase composition was investigated by means of optical and electronic microscope, rugosimetry and X-ray diffraction. Finally, electrochemical corrosion investigation was performed by means of Open Circuit Potential recording, Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy, to correlate coating structure corrosion resistance. P11 | 74 A RECHARGEABLE MAGNESIUM BATTERY BASED ON CHLOROALUMINATE IONIC LIQUIDS Federico Bertasia,b, Gioele Pagota, Keti Vezzùa, Enrico Negroa, Graeme Nawna, Antoine Bach Delpeucha, Riccardo Rigatoa, Sara Tonelloa, Giuseppe Pace,b Vito Di Notoa,b,* a Section of Chemistry for the Technologies, Department of Industrial Engineering, University of Padova, Via Marzolo 1, I-35131 Padova (PD), Italy, in the Department of Chemical Sciences. b CNR-IENI, Via Marzolo 1, I-35131 Padova (PD), Italy e-mail: [email protected] Mg-based secondary batteries are attractive candidates to satisfy the increasing global demand for efficient and safe energy storage systems.[1] Mg is able to provide a larger volumetric capacity compared with Li (3832 vs. 2062 mAh·cm-3);[1] and in addition, Mg batteries have a very good cyclability, lose little capacity over prolonged cycling, and have a wide temperature operation range.[2] One of the most important obstacles in the development of Mg-based secondary batteries is the lack of electrolytes that are capable of efficiently transporting magnesium ions without undergoing degradation, and whilst demonstrating good compatibility with the electrode materials (i.e., Mg metal at the anode and oxygen- or sulfur-based systems at the cathode).[3] The approach proposed in this work is to devise electrolytes based on an ionic liquid (IL) that is able to dissolve a suitable source of Mg ions.[4] ILs are a promising family of candidates for this type of application owing to their high chemical stability, low volatility and flammability, and remarkable capability to act as solvents. The proposed electrolytes consist of different amounts of δ-MgCl2 dissolved in a mixture of 1-Ethyl3-Methylimidazolium chloride (EMImCl) ionic liquid and aluminium trichloride, and are labelled as EMImCl/(AlCl3)m/(δ-MgCl2)n. The chemical composition of the electrolytes is determined by ICP-AES; the samples are investigated by high-resolution thermogravimetric analysis and modulated differential scanning calorimetry to determine the thermal stability and highlight the various phase transitions; the shortrange structure and interactions are elucidated by vibrational spectroscopy (both medium and far FT-IR). The electrochemical stability window is measured, and the applicability of the EMImCl/(AlCl3)m/(δ-MgCl2)n electrolytes in real devices is gauged by Mg stripping/plating measurements and full cell testing. Finally, the electrical response of EMImCl/(AlCl3)m/(δ-MgCl2)n electrolytes is studied by broadband electrical spectroscopy (BES). The integration of all the results allows to: (a) propose a reasonable conductivity mechanism; and (b) elucidate the complex interplay between the composition, the nanostructure and the electrical response. References [1] Piccolo, M.; Giffin, G. A.; Vezzù, K.; Bertasi, F.; Alotto, P.; Guarnieri, M.; Di Noto, V. ChemSusChem 2013, 6, 2157–2160. [2] Di Noto, V.; Fauri, M. Batterie primarie (non ricaricabili) e secondarie (ricaricabili) a base di elettroliti polimerici basati su ioni magnesio. PD99A000179, 1999. [3] Muldoon, J.; Bucur, C. B.; Gregory, T. Chem. Rev. 2014, 114, 11683–11720. [4] Bertasi, F.; Hettige, C.; Sepehr, F.; Bogle, X.; Pagot, G.; Vezzù, K.; Negro, E.; Paddison, S. J.; Greenbaum, S. G.; Vittadello, M.; Di Noto, V. ChemSusChem 2015, 8, 3069–3076. 75 | P12 STUDY OF SWIRL SHAPED DEFECTS IN HIGH EFFICIENCY N-TYPE SILICON SOLAR CELLS Simona Binetti,*,a Alessia Le Donne,a Valerio Folegatti,a Gianluca Colettib a Department of Materials Science and Milano-Bicocca Solar Energy Research Center (MIB-SOLAR), University of Milano-Bicocca, Via Cozzi 55, 20125 Milano, Italy b ECN Solar Energy, PO Box 1, NL-1755 ZG Petten, The Netherlands e-mail: [email protected] Industrial n-type Czochralski silicon (CZ-Si) solar cells with 20% of efficiency are known to experience an efficiency drop of about 1% absolute when swirl shaped regions with low lifetime (known as striations) are present. In spite an annealing process at low temperature was found to be partially effective to recover this efficiency loss [1], the nature of the defects responsible for the occurrence of striations is still unclear. In this work, n-type CZ-Si solar cells cut from ingots with different feedstock quality and oxygen content were analyzed in order to investigate the nature of the defects that give rise to striations. Microwave Photo-Conductance Decay (µW-PCD) maps demonstrated that striations are present in ingots with different feedstock quality, suggesting that no correlation exists between the typical low grade feedstock impurities and the occurrence of striations. µW-PCD maps showed as well that striations are present only in solar cells coming from top wafers of Si ingots with high oxygen content, suggesting the involvement of oxygen in the defects responsible for them. In good agreement with µW-PCD maps, photoluminescence (PL) spectra showed that a decrease of the intensity of the band-edge emission occurs on striations. Moreover, detailed temperature dependent PL analyses, demonstrated that a deep-level band around 0.87 eV grows up in the range between 15 and 110 K. The presence of oxygen precipitates in Si regions showing a strong emission at 0.87 eV was demonstrated in [2] by highly spatially resolved and highly sensitive secondary ion mass spectroscopy and by mapping of oxygen by luminescence activation using electron irradiation. Finally, temperature dependent PL analyses performed both outside striations and on samples coming from ingot with low oxygen content demonstrated the absence of the band at 0.87 eV. The involvement of oxygen, and in particular of oxygen precipitates, in the occurrence of striations seems therefore confirmed. References [1] G. Coletti, P. Manshanden, S. Bernardini, P.C.P. Bronsveld, A. Gutjahr, Z. Hu, G. Li, Solar Energy Materials and Solar Cells 2014, 130, 647 [2] M. Tajima, IEEE Journal of Photovoltaics 2014, 4(6), 1452 P13 | 76 DYE-SENSITIZED SOLAR CELLS BASED ON WATER-BASED ECO-FRIENDLY NATURE-INSPIRED DEEP EUTECTIC SOLVENT ELECTROLYTE SOLUTIONS Chiara Liliana Boldrini,a Norberto Manfredi,a Filippo M. Perna,b Vito Capriati,*b Alessandro Abbotto*a a Department of Materials Science and Solar Energy Research Center MIB-SOLAR, University of Milano-Bicocca, and INSTM Milano-Bicocca Research Unit, Milano, Italy b Dipartimento di Farmacia–Scienze del Farmaco, Università di Bari “Aldo Moro”, Consorzio Interuniversitario Nazionale “Metodologie e Processi Innovativi di Sintesi” C.I.N.M.P.I.S., Via E. Orabona 4, I-70125 Bari, Italy e-mail: [email protected] Among the new approaches to solar energy conversion, dye-sensitized solar cells (DSSCs) hold promise for high conversion efficiencies and low-cost manufacturing. Record efficiencies of 15% have been recently achieved. Unfortunately, one of the major drawbacks in these record cells is the presence of toxic volatile organic solvents in the electrolyte. Some efforts have been made in using water as the electrolyte solvent, but DSSCs proved to be typically unstable in this solvent. Thus, we have turned our attention towards not-hazardous, unconventional reaction media such as the deep eutectic solvents (DES). DES are combinations of two or three safe and inexpensive components which are able to engage in hydrogen-bond interactions with each other to form an eutectic mixture with a melting point much lower than either of the individual components.[1] Compared to traditional ionic liquids based on imidazolium salts which share low volatility with, DESs are simpler and cheaper to synthesize and do not need purification. In addition, DESs exhibit high electrochemical conductivity and are biodegradable. One of the most common DES components, choline chloride, is produced on the scale of million metric tons per year as an additive for chicken feed. DESs are thus attracting increasing interest in both academia and industry.[1] In this study we report our preliminary results on DSSCs containing water-based DES electrolytes, with water content up to 40%, sensitized by multi-branched phenothiazine dyes developed in our group.[2,3] Not only are DES-water-based DSSCs absolutely eco-friendly but also own superior stability over time due to the low volatility of these media. In particular, we have systematically varied the amount of I2 and I–, in the absence or presence of imidazolium salts and co-additives to improve current and photovoltage. Though efficiencies are still very modest, this unprecedented class of electrolytes is encouraging for both low cost and environmentally safe applications of solar cells. References [1] Smith, E. L.; Abbott, A. P.; Ryder, K. S. Chem. Rev. 2014, 114, 11060. [2] Review: Manfredi, N.; Cecconi, B.; Abbotto, A. Eur. J. Org. Chem. 2014, 7069. [3] Cecconi, B.; Manfredi, N.; Ruffo, R.; Montini, T.; Romero-Ocaña, I.; Fornasiero, P.; Abbotto, A. ChemSusChem 2015; dx.doi.org/10.1002/cssc.201501040. 77 | P14 INVESTIGATION OF THE PROMOTING EFFECT OF Mn IN STEAM AND AQUEOUS PHASE REFORMING OF GLYCEROL OVER Pt-Mn/C CATALYST Filippo Bossola,*a,b Vladimiro Dal Santob, Sandro Recchia,a Junming Sun,c Yong Wangd a Università degli Studi dell’Insubria, Via Valleggio 11, Como, Italy. CNR-Istituto di Scienze e Tecnologie Molecolari, Via Golgi 19, Milano, Italy. c Washington State University, Pullman, WA 99164, USA. d Pacific Northwest National Laboratory, 902 Battelle Blvd., Richland, WA 99352, USA. b e-mail: [email protected] Bimetallic heterogeneous catalysts are attracting in recent years much attention because they often show unique properties different from those of their parent metals, and that can be exploited for a wide range of industrial processes, such as the production of biofuels and hydrogen [1]. Pt-based catalysts have demonstrated to be very active in reforming reactions for H2 production due to their high C-C bond cleavage activity. The addition of Mn has been reported to have enhancing effect on the catalytic activity in reforming reaction [2], but there is a lack in the understanding of the promoting effect and reaction mechanism. In this work, a Pt and a Pt-Mn catalysts supported on activated carbon (TA60, PICATAL) were prepared by incipient wetness technique at the 3 wt.% (Pt-Mn molar ratio of 1), and characterized by BET, H2-TPR, XRPD and CO-pulse chemisorption. The catalysts were tested in the steam (SR) and aqueous phase (APR) reforming reactions of glycerol. The Pt-Mn catalyst showed comparable dispersion and only a slight increase in the reduction temperature compared to the Pt-based catalyst, suggesting that the two metals are in close contact. XRPD investigation confirmed these findings. The two reactions were carried out at 225 °C with a 10 wt.% glycerol/water solution. The GHSV in the SR reaction varied in order to achieve comparable conversion level (~20%). A bench Parr reactor Figure 1. Conversion and H2 TOF in SR. was used for the APR reactions. The major impact of Mn was on the SR reaction, where the TOF of H2 and the carbon conversion increased of about a factor of 7 and 4, respectively, whereas in the APR reaction the factors were only 1.6 and and 1.2, respectively. Noteworthy, in the SR reactions the hydrogen and CO selectivity decreased, as well as toward ethylene glycol, while acetol selectivity increased (Fig. 1). In the APR reactions, no major differences were found. These preliminary findings suggest that in the SR reactions the addition of Mn promotes the dehydration reaction pathway, probably due to the acidity generated by MnOx sites and/or to the weakening of the C–O bonds of the activated species, whereas in the APR reactions the liquid water suppresses these promoting sites. References [1] Dal Santo, V.; Gallo, A.; Naldoni, A.; Guidotti, M.; Psaro, R. Catal. Today 2012, 197, 190. [2] Kim H.; Park H. J.; Jeong K.; Lee C.; Kin C. Int. J. of Hydrogen En. 2012, 37, 8310. P15 | 78 Pt3Y ALLOY SYNTHESIS ON MESOPOROUS CARBON SUPPORT Riccardo Brandiele,a Christian Durante,a,* Emilia Grądzka,a Jian Zheng,a Gian Andrea Rizzi,a Gaetano Granozzi,a Armando Gennaroa a b Dept. of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova Institute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland e-mail: [email protected] One of the most promising technologies for the increasing demand of energy are the polymer electrolyte membrane fuel cell (PEMFC). The main challenge for the final commercialization of PEMFC is the cathode side oxygen reduction reaction (ORR), which is extremely slow also at the state of the art Pt base catalyst. Furthermore, the diffusion of Pt based catalyst is slowed down by the high cost and low availability of Pt. Recently, the preparation of Pt bimetallic systems has attracted considerable attention because the amount of Pt could be reduced while the catalytic activity and stability may be maintained or even improved, due to the so called "geometric effect" and "ligand effect". From theoretical calculations Pt3Y exhibits the second highest ORR activity ever measured on a polycrystalline electrode, surpassed only by single crystal Pt3Ni (111) e above all it has a catalytic activity greater than pure platinum.1,2 In this paper, we describe the synthesis and characterization of Pt3Y nanoparticles (NPs) supported on a commercial mesoporous carbon. Pt3Y NPs were synthesized by means of thermal reduction of suitable Pt and Y salt precursors in a tubular furnace. The effect of different salt precursors, the composition of the gas flow, reaction time and temperature on the resulting composition of the alloy and on the distribution and size of Pt3Y NPs were evaluated (Fig 1a). Finally, the catalytic activity towards ORR is reported and compared with a commercial standard confirming the increased activity of the Pt3Y alloy (Fig. 1b). a b Fig.1. (a) Tem image of Pt3Y on mesoporous carbon. (b) Linear sweep voltammetry on rotating disk electrode of Pt3Y|MC and the commercial standard Tanaka. References [1] P. Hernandez-Fernandez, F. Masini, D. N. McCarthy, C. E. Strebel, D. Friebel, D. Deiana, P. Malacrida, A. Nierhoff, A. Bodin, A. M. Wise, J. H. Nielsen, T. W. Hansen, A. Nilsson, I. E. L. Stephens and I. Chorkendorff, Nat. Chem., 2014, 6, 732–8. [2] V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P. N. Ross, C. a Lucas and N. M. Marković, Science, 2007, 315, 493–7. 79 | P16 STRUCTURAL AND MORPHOLOGICAL TUNING OF LiCoPO4 MATERIALS SYNTHESIZED BY SOLVO-THERMAL METHODS FOR Li-CELL APPLICATIONS Jessica Manzi, Mariangela Curcio, Sergio Brutti Dipartimento di Scienze, Università della Basilicata degli Studi della Basilicata, Via dell’Ateneo Lucano 10, 85100 Potenza, Italy e-mail: [email protected] Olivine-type lithium metal phosphates (LiMPO4) are promising cathode materials for lithium-ion batteries. LiFePO4 (LFP) is commonly used in commercial Li-ion cells but the Fe3+/Fe2+ couple can be usefully substituted with Mn3+/Mn2+, Co3+/Co2+ or Ni3+/Ni2+, in order to obtain higher redox potentials. In this poster we report a systematic analysis of the synthesis condition of LiCoPO4 (LCP) using a solvothermal route at low temperature [1], being the latter a valuable candidate to overcome the theoretical performances of LFP. In fact LCP shows higher working potential (4.8 V vs 3.6 V) compared to LFP and similar theoretical capacity (167 mAh g-1). Our goal is to show the effect of the synthesis condition of the ability of LCP to reversibly cycle lithium in electrochemical cells. LCP samples have been prepared through a solvothermal method in aqueous-non aqueous solvent blends. Different Co2+ salts have been used to study the effect of the anion on the crystal growth as well as the effect of solution acidity, temperature and reaction time. Materials properties have been characterized by fast-Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopies. The correlation between structure/morphology and electrochemical performances has been investigated by galvanostatic charge-discharge cycles. Reference [1] S. Brutti, J. Manzi, A. De Bonis, D. Di Lecce, F. Vitucci, A. Paolone, F. Trequattrini, S. Panero. Controlled synthesis of LiCoPO4 by a solvo-thermal method at 220 °C. Materials Letters (2015) 145. 324-327. P17 | 80 OPERANDO ELECTROCHEMICAL NMR MICROSCOPY OF POLYMER FUEL CELLS Alice S. Cattaneo a, Davide C. Villa a, Simone Angioni a,Chiara Ferrara a, Roberto Melzi b, Eliana Quartarone a, Piercarlo Mustarelli a a b Dept. of Chemistry and INSTM, University of Pavia, Via Taramelli 16, 27100 Pavia, Italy Bruker Biospin Italia, Viale Lancetti 43, 20158 Milano, Italy e-mail: [email protected] The implementation of operando measurements based on spectroscopic, microscopic and diffraction methods is emerging as a mandatory approach for full exploitation of the potential of functional materials and related electrochemical devices. During the last years, this approach was first applied to the investigation of materials for heterogeneous catalysis [1], and then to the investigation of lithium batteries [2]. Electrochemical reactions at solid-gas interfaces, which are of great interest for metalair batteries, water splitting devices and fuel cells, were also the object of careful studies [3-6]. Magnetic Resonance Imaging (MRI) at the microscopic level underwent fast development during ’90s and was rapidly recognized as a powerful tool for materials investigations. More recently, it was applied to the characterization of interfaces and full devices, even in operando conditions. Here, we give a feasibility proof of in operando 1H electrochemical NMR microscopy applied to polymer fuel cells. Our study is independent on the nucleus relaxation rates, without any relevant limitation on the operating temperature and actual humidity of the investigated device. This has been obtained thanks to a careful design of the experimental set-up and to the use of a new zero-time echo (ZTE) 3D acquisition sequence. Our results pave the way to the development of a powerful diagnostic approach to investigate water production and management also in fuel cells operating at high temperature and low humidity conditions, such as the ones designed for automotive. References [1] A. Vimont, F. Thibault-Starzyk, M. Daturi, Chem. Soc. Rev. 2010, 39, 4928. [2] X. Liu, et al., Nat. Commun. 2013, 4, 2568. [3] L. Li et al., Nat. Commun. 2015, 6, 6883. [4] G. Gershinsky, E. Bar, L. Monconduit, D. Zitoun, Energy Environ. Sci. 2014, 7, 2012. [5] Z.A. Feng, F. El Gabaly, X. Ye, Z.-X. Shen, W.C. Chueh, Nat. Commun. 2014, 5, 4374. [6] D.N. Mueller, M.L. MacHala, H. Bluhm, W.C. Chueh, Nat. Commun. 2015, 6, 6097 81 | P18 SYNTHESIS AND CHARACTERIZATION OF CROCONAINE DYES, A PROMISING CLASS OF NIR SENSITIZERS Cosimo Vincenzo Ciascaa, Vincenzo Finoa, Maria Annunziata Capozzia, Angela Punzia, Ambra Fiorea, Davide Vurroa, Gianluca Maria Farinolaa* Dipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, via Orabona 4, Bari, Italy [email protected] Near-infrared (NIR) absorbing dyes have gained increasing attention in the past few years1, especially because of their optoelectronic2 and biomedical application3. Among them, of particular interest are croconaine dyes that exhibit narrow and intense absorption bands in the near-infrared (NIR) region. Croconaines (Figure 1) are the superior homologues of the well-known squaraines, with a zwitterionic structure stabilized by resonance and characterized by a central electron acceptor system, the croconic acid and two donor terminal moieties either aromatic or eteroaromatic. The stronger electron-withdrawing ability of the croconic acid moiety with respect to squaric acid part produces a shift of about 100 nm in the absorption spectrum of croconaine dyes as compared with those of the corresponding squaraines4. This property, together with high molar extinction coefficients (ε > 105 M-1 cm-1) and good photostability make these molecules very attractive as NIR sensitizer. These dyes can be easily prepared by one-step condensation reaction between croconic acid and electron rich aromatic, heteroaromatic or olefinic compounds , which includes the azeotropic distillation of water during the reaction. The simplicity of this approach is of particular interest for the industrial scale up of these processes. Interestingly, computational study shows the possibility of directly anchor croconaines on titanium without the introduction of anchoring groups5, which further reduce the synthetic complexity. Here we report the synthesis of croconaine dyes having a series of differently substituted indole as donor units, with potential application as sensitizers in DSSC photovoltaic cells. Figure 1. Schematic representation of Croconaine dyes References [1] Y. Wu, W. Zhu Chem Soc. Rev. 2013, 42, 2039; [2] H. Kang, A. Facchetti, H. Jiang, E. Cariati, S. Righetto, R. Ugo, C. Zuccaccia, A. Macchioni, C.L. Stern, Z. Liu, S.T. Ho, E.C. Brown, M.A. Ratner, T.J. Marks J. Am. Chem. Soc. 2007, 129, 3267; [3] J. Chen, I.R. Corbin, H. Li, W. Cao, J.D. Glickson, G. Zheng J. Am. Chem. Soc. 2007, 129, 5798; [4] X. Zhang, C. Li, X. Cheng, X. Wang, B. Zhang, Sensors and Actuators B 2008, 129, 152 [5] A. L Puyad, Ch R. Kumar, K Bhanuprakash, J. Chem. Sci. 2012, 124, 1, 301. P19 | 82 INNOVATIVE AND FUNCTIONAL MATERIALS FOR GREEN AND SAFE Na-ION LARGE-SCALE ENERGY STORAGE Francesca Colòa, Giuseppina Meligranaa, Jijeesh R. Naira, Federico Bellaa, Andrea Lambertib, Matteo Destroc, Sonia Fiorillia, Paolo P. Pescarmonad, Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy b MPMNT Group, Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy c Lithops Batteries s.r.l., Via della Rocca 27, 10123 – Torino, Italy d Department of Chemical Engineering, University of Groningen, Nijenborg 4, 9747 AG Groningen, the Netherlands e-mail: [email protected] The modern life style that we are enjoying depends on energy storage systems in which the role of Li-ion batteries (LiBs) is peerless. However, state-of-the-art LiBs are approaching the verge of possible technological imagination in energy density. Some researchers argue that next-gen secondary batteries should switch to heavier elements such as Na. Indeed, when it comes to gigantic energy storage systems for the electricity grid and/or other non-portable applications where size does not matter, Na-ion batteries (NiB) can be an intelligent choice. Nevertheless, research on NiBs’ components is at the very beginning, and it is necessary to develop novel types of materials, both novel high energy electrodes and stable and safe polymer electrolytes. In this work, an overview is provided on both truly solid and quasi-solid polymer electrolytes specifically conceived and developed for Na-ion secondary cells, based on polyethylene oxide (PEO), acrylates/methacrylates and/or mixtures thereof. Eventually, pyranose ring based natural additives and/or low volatile plasticizers are added along with supporting sodium salts to improve specifically defined characteristics. Both standard casting and smart photopolymerization techniques have been explored [1,2]. Moreover, the most recent results regarding novel nanostructured negative electrodes, comprising TiO2 nanotubes, Ga2O3 nanorods and graphene-supported metal oxides will be presented. So far, work on Na-ion polymer batteries for moderate temperature application is at an early stage, only lab-scale small battery cells are demonstrated. The results about Ga2O3 nanorods and TiO2 nanotubes, along with the appropriate choice and development of novel polymer electrolytes, demonstrate that safe, durable and high energy density secondary Na-based polymer devices conceived for green-grid storage and operating at ambient and/or sub-ambient temperatures can be a reality in the near future. References [1] F. Colò, F. Bella, Jijeesh R. Nair, M. Destro, C. Gerbaldi, ElectrochimActa 174 (2015) 185190. [2] F. Bella, F. Colò, Jijeesh R. Nair, C. Gerbaldi ChemSusChem, 8 (2015) 3668-3676. 83 | P20 STEAM REFORMING OF CRUDE BIO-ETHANOL FOR HYDROGEN PRODUCTION OVER FP CATALYSTS Matteo Compagnoni, *,a Josè Lasso,a Alessandro Di Michele,b Ilenia Rossetti a a b Università degli Studi di Milano, Via C. Golgi 19, Milano, Italy Università degli Studi di Perugia,Via Pascoli, 06123 Perugia. e-mail: [email protected] The production of “bio-hydrogen” is an interesting alternative with respect the traditional production from hydrocarbons. In particular, the production from the bioethanol steam reforming process represent a promising route to improve its sustainability for energy-related purposes. The so-called 2nd generation bio-ethanol, derived from lignocellulosic biomass, such as sorghum, mischantus or poplars possibly growing in marginal lands, appears interesting. Unfortunately, the environmental and energetic impact of next generation biofuels depends on concentration, impurities and operative conditions. In this work two different bioethanol feeds, 50 and 90 vol%, supplied by Mossi&Ghisolfi Group (Proesa process), have been tested for low and high temperature steam reforming. Home-made prepared catalysts were employed in the catalytic tests. Ni was chosen as active phase and several supports were investigate (ZrO2, MxO-ZrO2, La2O3). The Flame spray Pyrolysis (FP) technique was employed for their synthesis. The steam reforming reaction was carried out at several temperature (300°C - 750°C) on a continuous micropilot plant. The effect of impurities was evaluated in term of catalyst performance because deactivation due to long chain alcohols (coke precursors) and sulfur represent key issues. At low temperature the use of bioethanol 90% showed almost the equal H2 productivity (1-1.2 mol min-1 kgcat-1) and ethanol conversion (100%) with respect pure ethanol[1]. By contrast, bioethanol with lower concentration (50%) induced different performance with an increase of coke deposition rate. The acidity of the support was tuned by using several oxidic supports, in order to prevent ethanol dehydration and coking through ethylene polymerization. Fresh and spent samples were characterized by XRD, TPR, TPO, TEM, FE-SEM and Raman analysis. Figure: scheme and image of Flame Spray Pyrolysis Reference [1] Rossetti, I.; Lasso, J.; Compagnoni, M.; De Guido, G.; Pellegrini, L.; Chem. Eng. Trans. 2015, 43, 229-234. P21 | 84 ELECTRODEPOSITION AND CHARACTERIZATION OF THIN FILMS OF MoS2 Andrea Comparinia, Ferdinando Capolupoa, Andrea Giaccherina, Maurizio Passapontia, Francesco Di Benedettob, Alessandro Lavacchic, Emanuele Piciollod, Massimo Cavallini,e Massimo Innocentia,c a Dipartimento di Chimica, Università di Firenze, via della Lastruccia 3, 50019, Sesto Fiorentino (FI), Italy. b Dipartimento di Scienze della Terra, Università di Firenze, via La Pira 4,50121, Firenze, Italy. c CNR, Istituto dei Composti Organometallici, via Madonna del Piano 10, 50019, Sesto Fiorentino (FI), Italy. d LEM S.R.L. Socio Unico, via L. Valiani, 55-59, 52021 Levane-Bucine (Ar), Italy. e CNR-ISMN, Via P. Gobetti, 101 40129 Bologna – Italy. e-mail: [email protected] The research more and more moves to discover low cost techniques to produce thin films of materials that have optimal characteristics to be used in solar cells. The Electrochemical Atomic Layer Deposition (E-ALD) [1] is one of these techniques that allows us to produce thin films of semiconductor. MoS2 is an important IV–VI type semiconductor, diamagnetic and with bandgap very close to silicon’s (1.7 eV), thus fitting perfectly with solar emission. Moreover, MoS2 with particle size in the range of 1–100 µm is a common dry lubricant. Few alternatives exist that confer high lubricity and stability up to 350°C in oxidizing environments [2,3]. E-ALD method was used to obtain semiconductor compounds in the form of thin films. The method is based on an alternate underpotential deposition of monolayer of the elements forming the compound. The UPD is a surface phenomenon that occurs when the deposition of one element precedes the massive electrodeposition. The UPD allows the perfect control of deposition of different kind of elements making possible to deposit highly defined nanostructures with a layer-by-layer control. The technical advantage is the possibility to modulate and to modify the parameters that influence the electrodeposition. That means that conditions for deposition can be adjusted concerning potential, pH, reactants and so on. UPD anodic electrodeposition of Na2S on crystalline Ag[111] electrode is well-known, so the research move to discover the optimal conditions to depose Mo on Ag/S from a solution of MoO42- in alkaline buffer. The UPD is a phenomenon limited by the surface of the electrode, so it’s possible to change the time of the deposition to confirm that just a monolayer is involved in faradic process. So, just using cyclic voltammetry, a very low coast technique, is it possible to have an high control of the process of deposition of the elements of interest. Our group of research have tried to study the optimal condition of deposition of Mo on Ag[111]/S in alkaline buffer. References [1] B. W. Gregory and J. L. Stickney, J. Electroanal. Chem., 300, 543 (1991). [2] G.L. Miessler, D.A. Tarr Inorganic Chemistry (3rd ed.)Pearson/Prentice Hall publisher, Harlow, England (2004) [3] D.F. Shriver, P.W. Atkins, T.L. Overton, J.P. Rourke, M.T. Weller, F.A. Armstrong Inorganic ChemistryW. H. Freeman, New York (2006). 85 | P22 SYNTHESIS AND PHOTOCHEMICAL PROPERTIES OF NEW MELANIN-INSPIRED ELECTROLUMINESCENT MATERIALS FOR OLED APPLICATIONS Valeria Criscuolo,a Paola Manini,a Alessandro Pezzella,a Pasqualino Maddalena,b Salvatore Aprano,c Maria Grazia Maglione,d Paolo Tassini,d Carla Minarini,d Marco d’Ischia a a Dept. Chemical Sciences, Univ. Naples Federico II, Complesso Universitario Monte S. Angelo, via Cinthia 4, I-80126 Naples, Italy. b Dept. Physics, Univ. Naples Federico II, Complesso Universitario Monte S. Angelo, via Cinthia 4, I80126 Naples, Italy. c SESMAT S.r.l., S.S.7 Appia 36, 82018, San Giorgio del Sannio (BN), Italy d Lab. Nanomaterials and Devices, ENEA C. R. Portici, p.le E. Fermi 1, I-80055, Portici (NA), Italy. e-mail: [email protected] In recent years increasing interest has been devoted to the synthesis of electroluminescent organic materials for the development of efficient organic lightemitting diodes (OLEDs) or light-emitting electrochemical cells (LEECs) for displays and lighting applications [1]. In the frame of a research line aimed at studying the potentiality of melanins in organic electronics [2], we report herein for the first time the synthesis of two different type of electroluminescent materials inspired to the melanin precursors 5,6-dihydroxyindole (DHI) and dopamine (DA). In particular, DHI has been used to prepare fluorescent asymmetric triazatruxenes (I) and DA has been involved in the synthesis of phosphorescent cyclometalated iridium(III) complexes (II) containing a novel set of 6,7-dihydroxy-3,4-dihydroisoquinoline ancillary ligands (DHQ) deriving from the catecholic neurotransmitter [3]. Reported is also a survey of the optoelectronic properties of I and II, both in solution and as thin films, and the fabrication and characterization of the corresponding OLED/LEEC devices. References [1] J. M. Fernandez-Hernandez, J. I. Beltran, V. Lemaur, M. D. Galvez-Lopez, C. H. Chien, F. Polo, E. Orselli, R. Fröhlich, Jeróme Cornil, and L. De Cola, Inorg. Chem. 2013, 52, 1812−1824 [2] P. Manini, V. Criscuolo, L. Ricciotti, A. Pezzella, M. Barra, A. Cassinese, O. Crescenzi, M. G. Maglione, P. Tassini, C. Minarini, V. Barone and Marco d’Ischia, ChemPlusChem 2015, 80, 919-927. [3] P. Manini, L. Panzella, I. Tedesco, F. Petitto, G. L. Russo, A. Napolitano, A. Palumbo, and Marco d’Ischia, Chem. Res. Toxicol. 2004, 17, 1190-1198 P23 | 86 SPLIT WITH RUST! MODIFIED HEMATITE PHOTOANODES FOR SOLAR WATER SPLITTING Nicola Dalle Carbonare,a,* Roberto Argazzi,b Stefano Caramori,a Carlo Alberto Bignozzia a Department of Chemical and Pharmaceutical Sciences, University of Ferrara, via Fossato di Mortara 17-27, 44121, Ferrara, Italy b ISOF/CNR c/o Department of Chemical and Pharmaceutical Sciences, University of Ferrara, via Fossato di Mortara 17-27, 44121, Ferrara, Italy email: [email protected] The ability to generate free energetic carriers under a suitable solar radiation designate to metal semiconductors an irreplaceable role in the development of solar water splitting technology. In this context, hematite (α-Fe2O3) has gained growing interest for the fabrication of photoanodes based on very cheap and abundant elements, due to its band gap of ca. 2.2 eV, a correct position of the Valence Band (VB) with respect to O2/H2O couple and a great stability in basic aqueous solution. Strategies to increase the water oxidation activity usually involve doping with various elements,[1] surface functionalization with oxygen evolving catalysts (OEC)[2],[3] and, more recently, in the introduction of nanometric oxide underlayer at the FTO back contact.[4] We report a series of successive functionalization of electrophoretic hematite photoanodes with different iron-oxide based structures. The introduction of a crystalline thin iron oxide layer at the contact between the FTO and the hematite film and the deposition of an amorphous iron catalyst (Fe-OEC) on the semiconductor surface produce a remarkable improvement of the photocurrent with respect to the native electrode, reaching ca. 1.5 mA cm-2 at 0.6 V vs SCE in basic medium.[5] DC photoelectrochemical characterization and Electronic Impedance Spectroscopy (EIS) are fundamental tools to clarify the effect on the charge separation and collection dynamic at the different interfaces of the modified electrodes. These results demonstrate that by combining different iron oxide morphologies, it is possible to improve the selectivity of the interfaces towards both electron collection at the back contact and hole transfer to the electrolyte, obtaining an efficient all-iron based photoelectrode entirely realized with simple wet solution scalable procedures. References [1] Sartoretti, C. J.; Alexander, B. D.; Solarska, R.; Rutkowska, W. A.; Augustynski, J.; Cerny, R. J. Phys. Chem. B 2005, 109, 13685. [2] Tilley, S. D.; Cornuz, M.; Sivula, K.; Grätzel, M. Angew. Chem. Int. Ed. 2010, 49, 6405. [3] Dalle Carbonare, N.; Cristino, V.; Berardi, S.; Carli, S.; Argazzi, R.; Caramori, S.; Meda, L.; Tacca, A.; Bignozzi, C. A. ChemPhysChem 2014, 15, 1164. [4] Le Formal, F.; Grätzel, M.; Sivula, K. Adv. Funct. Mater. 2010, 20, 1099. [5] Dalle Carbonare, N.; Carli, S.; Argazzi, R.; Orlandi, M.; Bazzanella, N.; Miotello, A.; Caramori, S.; Bignozzi, C. A. PCCP, 2015, 17, 29661. 87 | P24 EFFICIENT PHOTOINDUCED CHARGE SEPARATION IN A BODIPY-C60 DYAD Alessandro Iagatti,a,b Paolo Foggi,a,b,c Laura Bussotti,a Stefano Cicchi,d Stefano Fedeli,d Giacomo Biagiotti,d Massimo Marcaccio,e Eleonora Ussano,e Benedetta Mennucci,f Lorenzo Cupellini,f Stefano Capraseccaf, Mariangela Di Donatoa,b,d a LENS (European Laboratory for Non-Linear Spectroscopy) via N. Carrara 1, 50019 Sesto Fiorentino, Italy b INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125 Firenze, Italy c Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, 06100 Perugia, Italy d Dipartimento di Chimica ‘Ugo Schiff’, Università di Firenze, via della Lastruccia 13, 50019 Sesto Fiorentino, Italy e Dipartimento di Chimica ‘G, Ciamician’, Università di Bologna, via Selmi 2, 40126 Bologna, Italy f Dipartimento di Chinica e Chimica Industriale, Università di Pisa, via G. Moruzzi 13, 56124 Pisa, Italy e-mail: [email protected] A donor-acceptor dyad composed by a BF2-chelated dipyrromethene (BODIPY) and a C60 fullerene was newly synthetized and characterized. The two moieties were linked by direct addition of an azido substituted BODIPY[1] on the C60, producing an imminofullerene-BODIPY adduct. The photoinduced charge-transfer process in this system was studied by ultrafast transient absorption spectroscopy. Electron transfer towards the fullerene was found to occur both exciting the BODIPY chromophore at 500 nm and the C60 unit at 266 nm on a few picosecond timescale, but the dynamics of charge separation was different in the two cases. Eletrochemical studies provided information on the redox potentials of the involved species and spectroelectrochemical measurements allowed to unambiguously assign the absorption band of the oxidised BODIPY moiety, which helped in the interpretation of the transient absorption spectra. The experimental studies were complemented by a theoretical analysis based on DFT computations of the excited state energies of the two molecules composing the dyad and of their electronic couplings, which allowed to identify the charge transfer mechanism and rationalize the different kinetic behaviour observed by changing the excitation conditions. Reference [1] Fedeli, S., Paoli, P., Brandi, A., Venturini, L., Giambastiani, G., Tuci, G. and Cicchi, S. Chem. Eur. J., 2015, 21: 15349–15353. doi:10.1002/chem.201501817 P25 | 88 BICHROMOPHORIC CALIX[4]ARENE BASED SYSTEM FOR THE STUDY OF PHOTOINDUCED ELECTRON TRANSFER Federica Faroldi,a Aurora Sesenna,a Irene Tosi,a Laura Baldini,a Francesco Sansone a a Università degli Studi di Parma, Parco Area delle Scienze 17/A, Parma, Italy. e-mail: [email protected], Organic solar cells (OSCs) have gained the interest of researchers in the last few decades since they represent a low-cost sustainable energy source with low environmental impact. Understanding the photoconversion mechanism is fundamental for the design of efficient OSCs. In this context, our work is focused on the synthesis of two covalent electron donoracceptor pairs and on the study of the photoinduced electron transfer occurring between the two chromophores. We chose 2-hydroxy Nile Red as the donor and fullerene C60 as the acceptor. Nile Red is a well-known fluorescent and solvatochromic dye, which has been widely used as luminescent probe in the study of many chemical and biological systems and recently in the study of electron transfer with TiO2 colloidal nanoparticles [1]. Fullerenes, on the other hand, are characterized by high electron affinity and require small reorganization energy in the electron transfer processes. In addition, the presence of fullerene in a donor-acceptor dyad is able to promote long-lived chargeseparated states. We anchored the two chromophores at the upper rim of a cone calix[4]arene (compound 1), a convenient scaffold that allows the two moieties to be oriented in the same direction. Due to the residual flexibility of the structure, a modulation of the distance between the chromophores as a function of the medium could also be envisaged. The linear tri-components structure (2), composed by Nile Red-aromatic spacer-fullerene C60, was also synthesized as a reference compound to study the influence of the calixarene scaffold on the electron transfer process. 1 2 Figure 1. Target calix[4]arene 1 and reference compound 2. Reference [1] Anandan, S.; Yoon, M. Spectrochimica Acta Part A 2004, 60, 885-888. 89 | P26 PHOTOCATALYTIC ACTVITY OF NP-TIO2 SUPPORTED ON A NEW PERSISTENT LUMINESCENCE PHOSPHOR Maurizio Ferretti*a, Federico Locardia, Giorgio Andrea Costaa, Stefano Albertia, Ilaria Nellia, Valentina Carattob, Elisa Sanguinetib, Marco Fasolic,, Marco Martinic a Department of Chemistry and Industrial Chemistry, University of Genoa, Genoa, Italy Department of Earth, Environment and Life Sciences, University of Genoa, Genoa, Italy d Department of Materials Science, University of Milano-Bicocca, Milano, Italy b e-mail: [email protected] Probably the most used photocatalytic agent is the titanium dioxide in nanometric sizes. Recently, as alternative route for the efficiency increase, Li et al. proposed to support the TiO2 on the PeL materials to allow the photocatalytic process also in the absence of an external stimulation [1]. Specifically, using the luminescent material as internal “light” for the TiO2 excitation. The synthesized catalytic material tested in this work, is based on TiO2 nanoparticles supported on a new luminescent material. The first step involved the preparation of the luminescent material through a solid state synthesis between ZnO, Ga2O3, GeO2, Cr2O3. Differing from the literature [2], the raw powder were treated at 900°C for 2 hours, followed by a second heating at 1100°C for 2 hours. The TiO2 nanoparticles were prepared, as previous reported in our work [3], by a sol-gel method. The new catalyst was tested in the presence of a solution of methylene blue, demonstrating a high efficiency reaching a decomposition greater than 80% in 70 minutes. The novel catalyst was used both in the continuous presence of an external light excitation and alternating darkness/light conditions. The same degradation percentage of MB was obtained in both experiments demonstrating how during the dark interval the photoactivity was still present due to the persistent luminescent emission which provides the necessary photons to the TiO2. Consequently, a notable increment in the efficiency has been reached because using only half time of the external illumination the same degradation results were obtained. This work was supported by Italian Education Minister (MIUR), project number: PRIN 2012prot.2012ZELHLE References [1] Li H., Yin S., Wang Y., Sato T. J. Molec. Catal. A Chem. 2012, 363-364, 129-133. [2] Pan Z., Lu Y.Y., Liu F. Nature Mat. 2012, 11, 58-63. [3] Caratto V., Setti L., Campodonico S., Carnasciali M.M., Botter R., Ferretti M., J. Sol-Gel Sci. Tech. 2012, 63, 16-22. P27 | 90 PLASMONIC TiO2 THIN FILMS: INTERACTION BETWEEN Au NANOPARTICLES AND ORGANIC DYES FOR DSSC APPLICATIONS Daniele Franchi,a,b,c Bengt-Erik Mellander,b Maurizio Furlani,b Valeria Saavedra Becerril,d Massimo Calamante,a,c Alessandro Mordini,a,c Gianna Reginato,c Lorenzo Zani.c a Department of chemistry, University of Florence, Via della Lastruccia 13, Sesto Fiorentino, 50019, IT. Department of Applied Physics, Chalmers University of Technology, Göteborg, SE-41296, SE. c CNR - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, Sesto Fiorentino, 50019, IT. d Department of Physical Chemistry, Chalmers University of Technology, Göteborg, SE-41296, SE. b e-mail: [email protected] The introduction of metal nanoparticles into the nanoporous TiO2 structure of the photoanode layer in DSSCs can result in enhanced photocurrent depending on the dye and the nanoparticle characteristics. [1] The presence of gold nanoparticles (AuNPs) induces the plasmonic near-field absorption enhancement that allows the dye molecules located in their proximity to harvest more light increasing the quantity of electrons injected in the TiO2 layer and resulting in improved photocurrent. Among the various systems studied so far, AuNPs in combination with Ruthenium dyes have received increasing interest. [2] Our aim is to clarify the process behind the interaction between the dye and the AuNPs by means of steady-state and time-resolved spectroscopy of plasmonic TiO2 films sensitized with purely organic dyes. AuNPs are able either to be excited and inject electrons to the TiO2 conduction band (CB) or to be acceptors for electrons in the CB of TiO2, [3] the latter is a loss process for the DSSC, increasing the recombination rate. Gold is also sensible to corrosion if directly in contact with an iodine/triiodide-based electrolyte and might also promote recombination of the oxidized cationic dye with the injected electrons. These chemical and electronic interactions have been avoided creating a core-shell-shell Au-silica-titania system featuring an insulating silica shell between the Au and the TiO2. [4] Specific methodologies [5] were used to build up a shell thinner than 10 nm so that only the near-field electromagnetic interaction between the plasmon and the dye was allowed. Semitransparent TiO2 layers were needed to carry out the planned spectroscopic investigations. Highly homogeneous slurries of coated AuNPs/TiO2 and different methods of deposition and annealing were tested to optimize thin semitransparent films towards the desired properties. Spectroscopic characterization was carried out in solution and in thin film samples. The extent of absorption enhancement was investigated in various mixtures of organic dyes and AuNPs coated with different layers. References [1] Atwater, H. A.; Polman A. Nat. Mater. 2010, 9, 205. [2] Kawawaki, T.; Takahashi, Y.; Tatsuma T. J. Phys. Chem. C 2013, 117, 5901. [3] Primo, A.; Corma A.; García H. Chem. Chem. Phys. 2011, 13, 886. [4] Mc Farland, E. W.; Tang, J. A Nature 2003, 421, 616. [5] Sheehan, S. W.; Noh H.; Brudvig G. W.; Cao H.; Schmuttenmaer C. A. J. Phys. Chem. C 2013, 117, 927. 91 | P28 PEROVSKITE SOLAR CELLS STABILIZED BY CARBON NANOSTRUCTURES-P3HT BLENDS Simone Casaluci,a Teresa Gatti,*,b Francesco Bonaccorso,c Enzo Menna,b Aldo Di Carloa a CHOSE, Center for Organic and Hybrid Solar Energy, Dipartmento di Ingegneria Elettronica, Università di Roma “Tor Vergata”, via del Politecnico 1, 00133 Roma, Italia. b Dipartimento di Scienze Chimiche, Università di Padova, via F. Marzolo 1, 35123 Padova, Italia. c IIT, Istituto Italiano di Tecnologia, Graphene Labs, via Morego 30, 16163 Genova, Italia. e-mail: [email protected] Perovskite solar cells (PSCs) fabricated via two step deposition [1] have been prepared and tested using P3HT as the hole transport layer (HTL). P3HT was dissolved in chlorobenzene and blended with reduced graphene oxide nanoplatelets and single walled carbon nanotubes bearing on the external surface covalently bound paramethoxyphenyl substituents (RGO-PhOMe, SWCNT-PhOMe), aimed at improving their homogeneous mixing with the semiconducting polymer. The carbon nanostructures (CNSs) used for P3HT doping have been functionalized using aryl diazonium chemistry, keeping the amount of functionalities in a range which allows to gain better solubility but do not affect their electronic properties [2]. Caution was taken in order to obtain blends with no insoluble CNS residues, by applying a thorough protocol of sonication/centrifugation steps before spin coating the HTL on top of the hybrid junctions. Different weight percentages of functionalized CNSs/P3HT were deposed by spin coating in order to determine the optimum percentage. Such doping of the P3HT layer resulted in increased efficiencies and prolonged stabilities of the resulting PSCs with respect to devices with undoped P3HT HTLs. The best solar cells showed a power conversion efficiency (PCE) up to 11.7 % and an improved stability with respect to perovskite solar cells based on undoped P3HT. References [1] Casaluci, S.; Cinà, L.; Pockett, A.; Kubiak, P.S.; Niemann, R..; Reale, A.; Di Carlo, A.; Cameron, P.J. J. Power Sources 2015, 297, 504-510. [2] Salice, P.; Sartorio, C.; Burlini, A.; Improta, R.; Pignataro, B.; Menna, E. J. Mater. Chem. C 2015, 3, 303-312. P29 | 92 NEW POLYMERIC SINGLE-ION CONDUCTORS FOR RECHARGEABLE LITHIUM BATTERIES Luca Porcarellia, Alexander S. Shaplovb, Maitane Salsamendic, Jijeesh R. Naira, Federico Bellaa, Yakov S. Vygodskiib, David Mecerreyesc, Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 - Torino, Italy. b A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences (INEOS RAS), Vavilov str. 28, 119991, GSP-1, Moscow, Russia. c POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-San Sebastian, Spain. e-mail: [email protected] In recent years, wide research efforts have been devoted to the development of solid polymer electrolytes (SPEs) with the goal to enhance the intrinsic safety and replace the traditional flammable liquid electrolytes employed in the lithium-ion battery technology. Very commonly, SPEs are composed of a lithium salt dissolved either in a neutral polymer (e.g., PEO) or in an ion-conducting polymer matrix. The latter usually is represented by a new class of polyelectrolytes, namely poly(ionic liquid)s (PILs) [1,2]. Although significant progresses have already been achieved with cationic PILs, the motion of lithium ions carriers in such PIL/Li salt composite separators constitutes only a small fraction (1/5th) of the overall ionic current. This leads to the formation of a strong concentration gradient during battery operation, with deleterious effects such as favored dendritic growth and limited power delivery. Anionic PILs or polymeric single-ion conductors have been recently suggested as an alternative. Differently from other SPEs, a single-ion conductor is composed of a polymeric backbone bearing a covalently bonded anionic moiety and a Li counter-ion free to move and responsible for the ionic conductivity. Given the single-ion nature of the above-mentioned systems, the lithium-ion transport number is noticeably close to the unity. In this work, we present an innovative family of single-ion polymer electrolytes based on specifically developed lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1(trifluoromethanesulfonyl) imide ionic monomer. Varying the macromolecular architecture of the polyelectrolytes (i.e., random or block copolymers with poly(ethylene glycol) methyl ether methacrylate or crosslinked networks with poly(ethylene glycol)dimethacrylate) it was possible to develop the SPE with the tailored high ionic conductivity (up to 2.7×10-6 at 25 oC). A full overview of the electrochemical and thermal properties for the synthesized SPEs will be presented. Finally, the performance of prototype Li-ion batteries using the best PILs will be shown, which demonstrates their highly promising prospects as next-gen all-solid safe electrolytes. Acknowledgement. This work was supported by the Russian Foundation for Basic Research (project no. 14-29-04039_ofi_m) and by European Commission (project no. 318873 «IONRUN»). References [1] Yuan, J.; Mecerreyes, D.; Antonietti, M. Prog. Polym. Sci. 2013, 38, 1009. [2] Shaplov, A.S.; Marcilla, R.; Mecerreyes, D. Electrochim. Acta 2015, 175, 18. 93 | P30 A SIMPLE ROUTE TOWARDS NEXT-GEN GREEN ENERGY STORAGE BY FIBRE-BASED SELF-SUPPORTING ELECTRODES AND A TRULY SOLID POLYMER ELECTROLYTE Lorenzo Zolina,b, Jijeesh R. Naira, Federico Bellaa, Giuseppina Meligranaa, Pravin V. Jagdalec, Irene Cannavaroc, Alberto Tagliaferroc, Didier Chaussyb, Davide Beneventib, Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy b Grenoble Institute of Technology - Laboratory of Pulp and Paper Sciences (LGP2) – UMR, 5518 CNRS- Domaine Universitaire, 461 rue de la Papeterie, 38402 St. Martin d’Héres, France c MPMNT Group, Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy e-mail: [email protected] To meet the challenge of a green energy economy that could offer the chance to escape from our dependence on fossil fuels, the rapid development of materials science and technology is vital. Nowadays, advanced devices that convert and store energy are the focus of intensive research that is being carried out along various avenues and Lithiumion batteries (LIBs) in combination with fuel cells and supercapacitors hold the promise for a clean solution for an electric future. Currently, there are a number of efforts underway to develop lithium cells by using renewable resources, to simplify the fabrication processes to lower the costs, and to use water as solvent to reduce the environmental impact. An increased attention is also devoted to the recycling of spent LIBs even though the assessment of the real balance between the economic and environmental impact of this process is still matter of debate. In this respect, a novel and original Li-ion cell architecture is here successfully developed for the first time by exploiting the use of carbonized cellulose nanofibrils as both conductive binder and current collector substrate [1,2]. The cellulose nanofibrils are also used as a reinforcing agent for the preparation of an unconventional composite polymer electrolyte as separator [3]. The truly solid lab-scale Li-ion cell, assembled in a “pouch cell”, demonstrates remarkably stable cycling characteristics upon prolonged cycling at ambient temperature. The outstanding results are obtained along with the implementation of a pilot line procedure, comprising the spray coating and water-based papermaking techniques. Noteworthy, the battery components after use can be fully recovered using paper recycling techniques, which will definitely open up a truly new way of conceiving advanced sustainable batteries. References [1] L. Jabbour, C. Gerbaldi, D. Chaussy, E. Zeno, S. Bodoardo, D. Beneventi, J. Mater. Chem. 2010, 20, 7344. [2] D. Beneventi, D. Chaussy, D. Curtil, L. Zolin, E. Bruno, R. Bongiovanni, M. Destro, C. Gerbaldi, N. Penazzi, S. Tapin-Lingua, Chem. Eng. J. 2014, 243, 372. [3] Jijeesh R. Nair, L. Porcarelli, F. Bella, C. Gerbaldi, ACS Appl. Mater. Interf. 2015, 7, 12961. P31 | 94 IN-SITU SXRD STUDY OF THE E-ALD ELECTRODEPOSITION PROCESS OF Cu-S ULTRA-THIN FILMS SEMICONDUCTOR FOR SOLAR ENERGY CONVERSION Andrea Giaccherinia, Rosaria Anna Piccab, Maria Chiara Sportellib, Ferdinando Capolupoa, Giordano Montegrossic, Nicola Cioffib, Roberto Felicie, Francesco Carlàe, Alessandro Lavacchid, Francesco Di Benedettof, Massimo Innocentia a Chemistry Department, University of Firenze, Firenze, Italy. Chemistry Department, University of Bari “Aldo Moro”, Bari, Italy. c The Institute of Geosciences and Earth Resources, CNR, Firenze, Italy. d Institute of Chemistry of Organometallic Compounds, CNR, Firenze, Italy. e ESRF, Grenoble, Cedex, France 1f Department of Earth Sciences, University of Firenze, Firenze, Italy. b e-mail: [email protected] Scientific community is focusing attention on new compounds based on economic and low-environmental impact elements such as Cu, Sn, Fe and Zn; quaternary semiconducting materials based on the kesterite (Cu2ZnSnS4) mineral structure are among the most promising candidates as next generation of light-absorbing materials for thin-film solar cells. Surface limited electrodeposition of atomic layers metal chalcogenides can be performed exploiting Electrochemical Atomic Layer Deposition (E-ALD) technique to obtain sulfide ultra-thin films. In-situ Surface X-ray Diffraction (SXRD) measurements were performed at ESRF (Grenoble) and focused on the investigation of the growth mechanism of Cu-S ultra-thin films on the 111 crystal plane of a silver single crystal substrate, commonly used as a working electrode. The growth of the film was monitored by following the evolution of the Bragg peaks after each EALD step. Results point to the occurrence of a self-standing film with a definite crystal structure after 15 E-ALD cycles. After the Bragg reflections are observed for the first time, only minor changes of the structural arrangement are registered. Profile analysis of the Bragg peaks led to a qualitative interpretation of the growth mechanism, in the normal and in-plane directions, with respect to the Ag surface. Namely, the contribution of crystal strain and crystallite size were identified in the width of the Bragg reflections. The preliminary interpretation of the experimental reciprocal lattice, coupled to the Scanning Electron Microscopy (SEM) investigation, suggests that the samples show a pseudo single crystal diffraction pattern. This can be described by a new hexagonal unit cell. The crystal structure of this electro-deposited Cu2-xS could be related to that of chalcocite, in particular considering the layering of triangular Cu sites and octahedral Cu sites. The influence of the applied electric potential on the stability of the electrodeposited crystal structure was monitored by means of SXRD measurements performed without applying any potential, a structural change was, in fact, registered, and correlated to the occurrence of the stable phases under conventional laboratory conditions. 95 | P32 BAND GAP REVISED: A COMPUTATIONAL STUDY OF STRUCTURALLY RELATED POLY-THIOPHENES FOR PHOTOVOLTAICS a b c Davide Vanossi , Luigi Cigarini , Andrea Giaccherini , Massimo Innocentic, Claudio d Fontanesi a Department of Geological and Chemical Sciences, Via G. Campi 183, 41125 Modena, Italy Department of Physics, Via G. Campi 213, 41125 Modena, Italy c Department of Chemistry, Via della Lastruccia 3, 50019 Sesto Fiorentino, Firenze, Italy d Department of Engineering “Enzo Ferrari”, Via Vivarelli 10, 41125 Modena, Italy b e-mail: [email protected] Organic-inorganic p-n junction are well known as devices for the solar energy conversion, usually semiconducting polymers are used in p-n bulk heterojunctions as the p side. The n-side is constituted by inorganic materials, such as quantum dots, quantum well or bulk films as well as organic substrates. In this work a series of eight based polymers (donors) is considered, whose structures were designed to be suitably tuned with the electronic properties of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM).[1] The electronic properties of the mono-, di-, tri-meric thiophene oligomers are reckoned and compared to experimental spectroscopic and electrochemical results. The critical comparison of the experimental and theoretical HOMO LUMO band gaps suggest that electrochemical and DFT values are the most suitable values to be used in the design polythiophene-based p-n junction for photovoltaics. The discrepancy between electrochemical and spectroscopic measurements have been discussed, thus clarifying its arising. This discrepancy has been studied by Credi et al for quantum dots (QD).[2] Exploiting the analogy with QD, four different excitation mechanisms have been proposed, in order to develop a theoretical background for semiconducting molecules. Electrode polarization (electrochemical band-gap) or photon absorption (spectroscopic band-gap), involve different excitation mechanisms, thus they measure different phenomena, related by the exciton binding energy (Jeh). It is presented an understanding of the complementary information on the conduction/valence bands that can be provided by electrochemical oxidation/reduction potentials. On the ground of the theoretical description, their difference, seem to provide the values best suited for design and select optimum candidates for organic/hybrid photovoltaic systems. References [1] P. Morvillo, F. Parenti, R. Diana, C. Fontanesi, A. Mucci, F. Tassinari and L. Schenetti, Solar Energy Materials & Solar Cells, 2012, 104, 45. [2] M. Amelia, C. Lincheneau, S. Silvi and A. Credi, Chem. Soc. Rev., 2012, 41, 5728 P33 | 96 OIL PRODUCTION AS A DYNAMICAL SYSTEM L. Celi, *a C. Della Volpe,a S. Sibonia, L. Battistia, L. Pardi,b a b DICAM,UniTn, Trento, Italy. .IPCF-CNR, Pisa, Italy e-mail: [email protected], The behaviour of far-from-equilibrium and complex systems is one of the most intriguing phenomena of the recent science; natural and artificial systems offer a wide opportunity to this kind of analysis. The energy conversion is both a process based on important physical laws and one of the most important economy sectors; the interaction between these two aspects of the energy production offers an opportunity to apply some of the approaches of the dynamic systems analysis. In the present paper we try to develop an interpretation of the oil market history with the same methods used for complex physical systems. A phase plot, which is one of the methods to detect correlation between the quantities of a complex system, is proposed and a theoretical and experimental justification of such proposal in terms of the similarities of the thermodynamics and economics equation is illustrated[1]. The analysis is carried-out on the current data of oil production and market price[2]. A comparison of this approach with the common economic interpretation of the behaviour in terms of the standard marginal theory [3] is also shown. oil industry phase plot - BP data 100 '10 limit the china problem forbidden by technology, technology limit values not allowed with '80 tech '80 limit, the american peak 60 forbidden by technology, technology limit values not allowed by '10 tech US dollar 2010 per barrel (Brent dated) 80 40 20 toward "the peak" the absolute peak zone this zone is forbidden by market competition this zone is forbidden by economic convenience, it is below production cost; new investments allow a lower price 0 1500 2000 2500 3000 3500 million ton /year References [1] Saslow W.M. Am. J. Phys. 1999, 50, 12 [2] BP Statistical Review of World Energy 2014 [3] Murray J. and King D. Nature, 2012, 481, 433 4000 4500 97 | P34 FIXED ENERGY X-RAY ABSORPTION VOLTAMMETRY FOR INVESTIGATION OF REACTION MECHANISM IN ALKALINE DIRECT ALCOHOL FUEL CELLS W. Giurlania, A. Lavacchib, C. Zafferonia, A. Giaccherinia, A. De Lucaa, G. Montegrossic, F. Di Benedettoc,d, F. d'Acapito,e M. Innocentia,b a Dipartimento di Chimica, Università di Firenze, via della Lastruccia 3, 50019, Sesto Fiorentino (FI), Italy. b CNR, Istituto dei Composti Organometallici, via Madonna del Piano 10, 50019, Sesto Fiorentino (FI), Italy. c CNR, Istituto di Geoscienze e Georisorse, via G. La Pira, 4, 50121, Firenze (Italy) d Dipartimento di Scienze della Terra, Università di Firenze, via La Pira 4,50121, Firenze (Italy). e CNR, Istituto di Officina dei Materiali, OGG, c/o ESRF, Grenoble (France) e-mail: [email protected] Fuel cells are gradually taking place worldwide in the energetic panorama. Alkaline Direct Alcohol Fuel Cells (ADAFC) are especially interesting for two reasons: first, they allow using other catalysts than the expensive platinum; then, in addition to producing energy, they provide, in case of partial oxidation, interesting products for industrial applications. To improve and understand in depth such devices, it is of paramount importance the investigation of the reaction mechanism that occurs on the electrode’s surface. Fixed Energy X-ray Absorption Voltammetry (FEXRAV) represents an innovative, fast and easy[1] technique for the in situ X-ray absorption analysis. The energy is fixed near the X-ray white line in order to give the greatest contrast between the different oxidation states of the element. The measurement is taken recording the changing of absorption and/or fluorescence intensity while the electrode potential varies. In this way, it is possible to perform conventional electrochemical methods and follow the transition between different valence states and the coordination environments of the elements under observation at the same time. The in operando study allows to point out intermediate oxidation states, adsorption species and structural and morphological changing that are not visible in an ordinary cyclic voltammetry; so from all these information it’s possible extrapolate an hypothesis about the reaction mechanism. All the experiments have been performed on fuel cells for the study of Pd catalyst supported on carbon as anode in solution of KOH, KOH + EtOH and KOH + HCOOon LISA Beamline (BM08, ex-GILDA) in the synchrotron of Grenoble. References [1] Minguzzi, A.; Lugaresi, O.; Locatelli, C.; Rondinini, S.; D’Acapito, F.; Achilli, E.; Ghigna, P. Anal. Chem. 2010, 85, 7009-7013. P35 | 98 EFFECT OF TRIALKOXYSILANE GROUP LINKER ON PHOTOINDUCED CHARGE INJECTION ON TIO2 NANOSTRUCTURED FILMS Alessandro Iagattia,b*, Mariangela Di Donatoa,b,c, Sandra Doriaa, Marco Moninic, Daniele Franchic, Massimo Calamantec,d, Lorenzo Zanid, Adalgisa Sinicropie, Gianna Reginatod, Paolo Foggia,b,f a European Laboratory for Non Linear Spectroscopy (LENS), Universita` di Firenze, via Nello Carrara 1, 50019 Sesto Fiorentino, Florence, Italy b INO-CNR, Istituto Nazionale di Ottica – Consiglio Nazionale delle Ricerche, Largo Fermi 6, 50125 Florence, Italy c Università degli Studi di Firenze, Dipartimento di Chimica “Ugo Schiff”, Via della Lastruccia 13, 50019 Sesto Fiorentino, Italy d CNR-Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy e Universita degli Studi di Siena, Dipartimento di Biotecnologie, Chimica e Farmacia, Via A. Moro 2, 53100 Siena, Italy f Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy e-mail: [email protected], Dye-sensitized solar cells (DSSCs) have attracted notable interest in the last few years as effective low-cost devices for solar energy conversion. In these systems a dye molecule, adsorbed on a nano-crystalline thin-film semiconductor through a molecular bridge, harvests solar energy and transfers electrons into the semiconductor conduction band. We have analyzed the excited state dynamics of two novel organic dyes that differ for the presence of carboxylate (DF15) and trialkoxysilane (MM35) as linkers group. The spectroscopic properties of the two dyes were studied both in solution and when adsorbed on TiO2 and ZrO2 nanoparticle using both stationary and time-resolved techniques, probing the sub-picosecond to nanosecond time interval. The comparison between the solution and the solid substrate data allows us to identify different pathways of the energy and electron relaxation. The transient spectra of the TiO2 adsorbed dyes show the appearance of a long wavelength excited state absorption band, attributed to the cationic dye species, which is absent in the spectra measured in solution or when the dye is absorbed on ZrO2 film. Furthermore, the kinetic traces of the samples adsorbed on TiO2 film show a long decay component not present in solution and ZrO2. The slowdown of the ground-state recovery time is the indirect evidence of the electron injection on the semiconductor conduction band. The interpretation of the experimental results has been supported by theoretical DFT calculations of the excited state energies and molecular orbitals of the analyzed dye molecules. 99 | P36 MANGANESE COMPLEXES AS REDOX MEDIATORS IN DYE SENSITIZED SOLAR CELLS Stefano Carlia, Elisabetta Benazzi*a, Laura Casarina, Stefano Caramoria, Roberto Argazzi, Carlo Alberto Bignozzia. a Department of Chemistry and Pharmaceutical Sciences and bCNR-ISOF c/o Department of Chemistry and Pharmaceutical Sciences, University of Ferrara, Via Fossato di Mortara 17, 44121 Ferrara, Italy e-mail: [email protected] The photoelectrochemical properties and stability of dye sensitized solar cells containing Mn(β-diketonato)3 complexes, [MnIII(acac)3] (acac = acetylacetonate), [MnIII(CF2)3] (CF2 = 4,4-difluoro-1-phenylbutanate-1,3-dione), [MnIII(DBM)3] (DBM = dibenzoylmethanate), [MnII(CF2)3]TBA (TBA = tetrabutylammonium) and [MnII(DBM)3]TBA, have been evaluated1. At room temperature, the complexes undergo ligand exchange with 4-tert-butyl-pyridine (TBP), an additive commonly used in the solar device to reduce charge recombination at the photoanode. An increased device stability was achieved by using the Z907 dye and passivating the photoanode with short chain siloxanes. It was also found that, for this class of compounds, the Mn(II)/(III) couple is involved in the dye regeneration process, instead of Mn(III)/(IV) (E1/2 > 1V Vs SCE) previously indicated in the literature2. Moreover other Manganese complexes, in which the Mn(III)/Mn(IV) couple is involved in dye regeneration, have been investigated in order to improve the chemical and electrochemical stability. In particular, we found that encapsulating (N4O2) Shiff base ligands3 lead to Mn(III) complexes that are high stable even in presence of TBP and studies are in progress toward both the optimization of the electrolyte composition and the photoanode surface passivation. References [1] Carli, S.; Benazzi, E.; Casarin, L.; Bernardi, T.; Bertolasi, V.; Argazzi, R.; Caramori, S.; Bignozzi, C. A. Phys. Chem. Chem. Phys., 2015, accepted manuscript. [2] Perera, I. R.; Gupta, A.; Xiang, W.; Daeneke, T.; Bach, U.; Evans, R. A.; Ohlin, C. A.; Spiccia, L. Phys. Chem. Chem. Phys. 2014, 16, 12021. [3] Panja, A., Eur. J. Inorg. Chem. 2003, 8, 1540. P37 | 100 MATERIALS AND METHODS FOR ENERGY HARVESTING IN THE SHOES INDUSTRY Fabio Invernizzi*a, Leonardo Lanfredia, Maddalena Patrinib, Sergio Dulioc, Piercarlo Mustarellia a Department of Chemistry of the University of Pavia, and INSTM, Via Taramelli 16, 27100 Pavia, Italy Department of physics of the University of Pavia, Via Bassi 6, 27100 Pavia, Italy c Atom S.p.A., Via Morosini 6, 27029 Vigevano, Italy b e-mail: [email protected] The rapid technological developments in the last years led to the invention, tuning and subsequent commercialization of many types of electronic devices (e.g. smartphones) that have become really useful, if not indispensable, during our day live. These devices are more and more demanding from the energetic point of view, and the state-of-the-art batteries have not enough energy density to allow their continuous usage. Energy harvesting from human gait is a promising way to produce energy when far from stationary supply systems. Many movements can be exploited to harvest energy, J. M. Donelan and co-workers developed a device that convert energy from the bending of legs [1], whereas Wang et al. focused their attention on the movement of the arms [2]. Krupenkin and Taylor [3] exploited human walk to produce energy form the pressure of the foot on the ground. In this paper we analyze the approaches to harvest energy from the walk, focusing on the principles of operation as well as on the materials involved in the processes. We also present some preliminary results on a harvesting method currently under study at our laboratory. References [1] J. M. Donelan et al, Science 319, 2008, 5864, 807-810 . [2] Wang Z. L. ,Adv. Mater. 2012, 24, 1759–1764 [3] Krupenkin, T. & Taylor, J.A., Nat. Commun. 2011, 2, 448, doi: 10.1038/ncomms1454 101 | P38 A POLARIZABLE QM/CLASSICAL APPROACH FOR THE MODELLING OF ELECTRONIC ENERGY TRANSFER IN EMBEDDED SYSTEMS Sandro Jurinovich, Benedetta Mennucci Department of Chemistry, University of Pisa, Via Risorgimento 13, Pisa, Italy e-mail: [email protected] The energy transfer processes in multichromophoric systems are at the basis of the behavior of natural, bio-hybrid and artificial antennae.[1-3] Electronic Energy Transfer (EET) is the physical process allowing the migration of the absorbed energy over reasonably large distances. EET process is determined by both the interaction between the chromophores and those of each chromophore with the surrounding environment. From a theoretical point of view, one of the fundamental quantities to model EET is the excitonic Hamiltonian of the coupled system, which describes how the excitation energy is shared among the different units. Here we present a multiscale QM/classical approach to model the exciton Hamiltonian of a multichromophoric system with the inclusion of the environmental effects by adopting a polarizable embedding scheme for the classical part. An accurate evaluation of the electronic coupling based on a transition density matrix approach is presented. Moreover, thanks to the polarizable embedding, explicit environmental effects (screening or enhancement effects) are naturally included in the calculation. Different applications are presented: from bridge-mediated EET in simple donoracceptor dyads [4] to more complex natural light-harvesting (LH) systems. In the latter case the QM/classical strategy for the modeling of electronic processes is coupled with classical molecular dynamics simulations to capture both structural and electrostatic dynamical effects.[5] References [1] Saikin, K. S.; Eisfeld, A.; Valleau S.; Aspuru-Guzik, A. Nanophotonics 2013, 2, 224. [2] Harriman, A. ChemComm 2015, 51, 11745. [3] Peng, H; Niu L.; Chen, Y; Wu, Z; Tung, C; Yang, Q. Chem. Rev. 2015, 115, 7502. [4] Caprasecca, S.; Curutchet, C.; Mennucci, B. J. Chem. Theo. Comput. 2012, 8, 4462. [5] Jurinovich, S; Viani, L.; Curutchet, C; Mennucci, B. Phys. Chem. Chem. Phys. 2015, 14, 11657. P39 | 102 ELECTROSPUN HYBRID GEL POLYMER ELECTROLYTE FOR LITHIUM BATTERIES Catia Arbizzania, Francesca De Giorgioa, Davide Fabianib, Maria Letizia Focaretea, Andrea La Monacaa, Marco Zaccariab a Alma Mater Studiorum Università di Bologna, Dipartimento di Chimica “Giacomo Ciamician”, via Selmi 2, 40126, Bologna, Italy b Alma Mater Studiorum Università di Bologna, Dipartimento di Ingegneria dell'Energia Elettrica e dell'Informazione "Guglielmo Marconi", Viale Risorgimento 2, 40136 Bologna, Italy e-mail: [email protected] Safety is one of the major concerns of lithium batteries: lithium dendrite growth during repeated charge/discharge cycles and solid polymer electrolytes (SPEs), with the dual function of separator and electrolyte, hinders this phenomenon that causes hazardous short circuits [1]. Polyethylene oxide (PEO), together with a lithium salt, was a promising candidate as SPE, thanks to its good mechanical and electrochemical properties. However, its low ionic conductivity at room temperature is a severe drawback. In the last years gel polymer electrolytes (GPEs) have gained great attention for applications in lithium batteries for the high ionic conductivity at room temperature, good mechanical properties and safety improvements [2]. GPEs can consist of a flexible polymeric matrix as supporting network and a liquid phase, containing a lithium salt, which conduct ions [3]. Several polymers, like polyvinylidene difluoride (PVdF) for the high dielectric constant and the good electrochemical stability, and PEO have been used as matrix for GPEs. Given the good compatibility between PVdF and PEO, we prepared and characterized hybrid gel polymer electrolytes (HGPEs), based on polymeric blends PVdF/PEO soaked in the liquid electrolyte with lithium salt, with the aim to merge the properties of these two polymers. Electrospinning was chosen as method to prepare the polymeric blends. This technique yields micro-nanofibrous membranes with high porosity and, therefore, huge values of electrolyte uptake [4]. Two blends with the same composition (PVdF:PEO, 90:10 w/w) were prepared using PEO of different molecular weight (Mv 100,000 and 1,000,000) and soaked in 1M LiPF6 – ethylene carbonate:dimethyl carbonate (1:1 w/w). The electrochemical performance of the two blends were tested in a Li/HPGE/LiFePO4 cell and discussed on the basis of their physical, mechanical, thermal and morphological properties. Acknowledgments Alma Mater Studiorum –Università di Bologna is acknowledged for RFO financial support References [1] Croce, F.; Focarete, M. L.; Hassoun, J.; Meschini, I.; Scrosati, B. Energy Environ. Sci. 2011, 4, 921-927 [2] Manuel Stephan, A. European Power Journal 2006, 42, 22. [3] Marcinek, M.; Syzdek, J.; Marczewski, M.; Piszcz, M.; Niedzicki, L.; Kalita, M.; PlewaMarczewska, A.; Bitner, A.; Wieczorek, P.; et al. Solid State Ionics 2015, 276, 115. [4] Zaccaria, M.; Fabiani, D.; Cannucciari, G.; Gualandi, C.; Focarete, M. L.; Arbizzani, C.; De Giorgio, F.; Mastragostino, M. J. Electrochem. Soc. 2015, 162, A915. 103 | P40 INTEGRATED POWER TO GAS PROCESSES: TECHNICAL AND ECONOMICAL FEASIBILITY Grazia Leonzioa a Department of Industrial and Information Engineering and Economics, University of L'Aquila, Via Giovanni Gronchi 18, 67100 L'Aquila, Italy; e-mail: [email protected]; The Power-to-Gas process chain could play a significant role in the future energy system. Renewable electric energy can be transformed into storable methane via electrolysis and subsequent methanation, through the Sabatier reaction: The resulting CH4, known as synthetic methane, can be injected into the existing gas distribution grid, or it can easily be utilized in all cogeneration system to produce electricity and heat. In this research a feasibility study of biogas plant integrated with power to gas system is carried out. In Sabatier reaction the CO2 is obtained from biogas while H2 from electrolyze using wind energy for the production of electricity. In addition to methane produced by reaction, bio-methane from upgrading of biogas can be stored and send in the cogeneration system or in the network. To have an integrated power to gas plant with 1000 kWe it is necessary to have the operating conditions reported in table 1. Different integrated solutions are evaluated: a-energy electricity produced by bio-methane obtained with biogas upgrading and synthetic methane; benergy electricity produced by only synthetic methane without biogas upgrading; cimmision to network of bio-methane obtained with biogas upgrading and synthetic methane; d-immision to network of synthetic methane without biogas upgrading. Economical incentives are calculated according the directive 2013/12/5 [1]. Infect the economic feasibility of this plants is strongly depended on CAPEX (investment, cost of money and required payback time) and the prices of electricity, methane and oxygen, which is inevitable by-product from electrolysis [2]. Table 1 Operating parameters of integrated power to gas system and economical incentives Operating parameters Electrical power of integrated system Thermal power of integrated system Efficiency of cogeneration system Methane flow-rate Carbon dioxide flow-rate Hydrogen flow-rate Efficiency of electrolyzer Electricity power from renewable (wind energy) 1000 kWe 2500 kWt 40 % 10 kmol/h 4,6 kmol/h 22 kmol/h 75 % 1980 kW Economical incentives Energy electricity produced by synthetic methane and bio-methane Energy electricity produced by synthetic methane Immision to gas network of synthetic methane and bio-methane Immision to gas network of synthetic methane 787.000 €/year 778.000 €/year 404.000 €/year 406.000 €/year Results show that the first solution allow to have the higher economical incentives equal to 787.000 €/year. References [1] Maes, D.; Dael, M.V.; Vanheusden, B.: Goovaerts, L.; Reumerman, P.; Luzardo, N.M.; Passel, S.V.; Journal of Cleaner Production. 2015, 88, 61-70. [2] Breyer, C.; Tsupari, E.; Tikka, V.; Vainikka, P.; 9th International Renewable Energy Storage Conference (IRES 2015), Düsseldorf 2015, March 9–11, 2015. P41 | 104 ENVIROMENTAL ANALYSIS OF PROCESSES TO PRODUCE BIO-METHANE Grazia Leonzioa a Department of Industrial and Information Engineering and Economics, University of L'Aquila, Via Giovanni Gronchi 18, 67100 L'Aquila, Italy; e-mail: [email protected]; For a biogas upgrading technology, both energy consumption and environmental impact are critical screening criterion. Compared to energetic analysis, the environmental impact assessment for biogas upgrading process is relatively fewer [1]. In this research a comparison between upgrading technologies of biogas to bio-methane is carried out. Purification systems of biogas with CO2 remove through chemical absorption, power to gas (bio-methane is used to produce electrical energy or send to gas network) are compared. The Life Cycle Assessment software GaBi® v. 6.3 is used following the ISO 14040 with this goal. The functional unit is defined as generation of 1 MJ of bio-methane obtained from anaerobic digestion. The system boundaries include processes necessary to this purpose while the material and energy balances obtained from ChemCad 6.3® simulations are used for Life Cycle Inventory analysis [2]. Co-products and by-products are not produced during simulation, so there are not allocation problems. CML 2001-Apr. 2013 methodology has been used to estimate the environmental impacts, during classification and characterization of the results of the life cycle inventory analysis, using the Ecoinvent 2.2 database. Table 1 shows the obtained results for each impact categories [2]. Table 2 Results of Life Cycle Assessment analysis for upgrading of biogas to bio-methane Chemical absorption GWP (kgCO2 eq) ADPEF (kgSb eq) AP (mol H+ eq) EP (mol di N eq) ODP (kgCFC11 eq) Human tox (cancer) (CTUh) Human tox (non cancer) (CTUh) Particular matter (PM2,5 eq) Ionising radiation (kgU235 eq) POCP (kgNMVOC) EP water (kgP eq) Eco tox (CTUe) Power to gas KOH solution NaOH solution MEA solution Feed by biogas purification Feed not by biogas purification Immision to gas network 1.62∙105 0.043 791 2.73∙103 4.11∙10-6 3.11∙10-3 0.0328 43.1 3.07∙104 6.61∙102 5.10∙101 1.18∙105 1.62∙105 0.043 791 2.73∙103 4.11∙10-6 3.11∙10-3 0.0328 4.32∙101 3.07∙104 6.61∙102 5.10∙101 1.18∙105 1.62∙105 0.043 791 2.73∙103 4.11∙10-6 3.11∙10-3 0.0328 4.32∙101 3.07∙104 6.61∙102 5.10∙101 1.18∙105 4.90∙105 0.34 1.48∙103 4.86∙103 2.83∙10-5 1.99∙10-4 0.0252 96.3 5.16∙105 1.06∙103 1.47 2.10∙104 4.90∙105 0.34 1.48∙103 4.86∙103 2.83∙10-5 1.99∙10-4 0.0252 96.3 5.16∙105 1.06∙103 1.47 2.10∙104 4.90∙105 0.34 1.48∙103 4.86∙103 2.83∙10-5 1.99∙10-4 0.0252 96.3 5.16∙105 1.06∙103 1.47 2.10∙104 Results show that the purification processes with chemical absorption allow to save more CO2 emissions as reported in literature [3]. In this case the incineration system cause more CO2 emissions equal to 36%. The production of thermal energy from natural gas and the production of electricity follow respectively with 55% and 9%. In power to gas processes emissions are related mainly to water hydrolysis. For AP, ADPEF, GWP, particular matter, ionising radiation, POCP, ODP the minor consumption of electrical energy determine the minor environmental impact. EP and human tox are relevant in chemical absorption as for eco tox due to electrical production. References [1] Starr, K.; Gabarrell, X.; Villalba, G.; Talens, L.; Lombardi, L.; Waste Manag. 2012, 32 (5) 991–999. [2] Leonzio, G.; Journal of chemical production. 2016, Under review. [3] Starr, K.; Peiro, L.T.; Lombardi, L.; Gabarrell, X.; Villalba, G.; Journal of Cleaner Production. 2014, 76, 32-41. 105 | P42 SUITABLE ENVIRONMENTAL REFRIGERATION FOR PHOTOVOLTAIC/THERMAL SYSTEM IN DUBAI Grazia Leonzio,a a Department of Industrial and Information Engineering and Economics, University of L'Aquila, Via Giovanni Gronchi 18, 67100 L'Aquila, Italy; e-mail: [email protected]; Solar energy is an renewable energy source and is used since decades for producing both electricity and heat also simultaneously through photovoltaic/thermal collectors according the European regulation [1]. The operating temperature of PVT is an important key-point for the system: while higher operating temperatures increase the potential use of the co-generative heat, they decrease the electricity production. As a consequence, researchers are performing a special effort towards refrigeration system providing medium-temperature heat (60–80 °C) at high electrical efficiency. Studies have also shown that high temperature can cause long term degradation of cells. Usually cooling systems of photovoltaic/thermal system are classified as passive and active. The development of micro- and nano-technologies offers new perspective and efficient innovation strategies that integrate environmental concerns are also used [2]. In this research an energetic and environmental analysis is carried out to establish the better refrigeration system among cooling tower, refrigeration cycle, phase change material, absorption heat pump in a Dubai plant. To this purpose a new parameter, energetic and environmental gain, is used; energetic is electrical power of panel/consumption of electrical energy; environmental is CO2 emissions saved with the use of panel/CO2 issued with consumption of electrical energy. Results shows that this values are coincident. Figure 1 shows as the integration with absorption heat pump with one effect is the better solution: the system has the minor consumption of electrical energy and CO2 emissions. In addition for an innovations and creative solutions for more sustainable activities the cold produced by heat pump in evaporator can be used for the refrigeration of panel: the same system provide the more refrigeration load. The one effect absorption heat pump is the better solution for sustainable environmental performance in Dubai, saving more CO2 emissions. Figure 3 Energetic and environmental gain of refrigeration systems Figure 2 CO2 emissions of refrigerant systems Figure 3 Additional refrigeration load produced by integrated system References [1] Directive 2009/28/EC of the European Parliament and of the Council of 23 April 2009 on the promotion of the use of energy from renewable sources and amending and subsequently repealing Directives 2001/77/EC and 2003/30/EC; April 23, 2009. [2] Micheli, L.; Sarmah, N.; Luo, X.; Reddy, K.S.; Mallick, T.K.; Renewable and Sustainable Energy Reviews 2013, 20, 595–610. P43 | 106 MODELING OF PHOTOVOLTAIC/THERMAL SOLAR PANEL Grazia Leonzioa a Department of Industrial and Information Engineering and Economics, University of L'Aquila, Via Giovanni Gronchi 18, 67100 L'Aquila, Italy; e-mail: [email protected]; Solar energy is inexhaustible and import-independent resource that enhances energy security and sustainability, reduces pollution, lowers the cost of mitigating climate change. Photovoltaic/thermal (PVT) technologies employ the photovoltaic effect to convert solar energy into electricity and heat. PVT technologies are rapidly becoming an important component of the energy landscape. In fact PVT is the third most important renewable energy source in terms of globally installed capacity [1]. In this work a model for PVT system is presented through COMSOL Multiphysics™ 4.2 software in order to have the profiles of temperature and velocity of refrigerant fluid (water). Refrigeration, in fact, is an important key point for the system. The evaluated panel consists of monocrystalline silicon cells that are bound with a silicone thermal paste to an aluminum reservoir through which coolant water flows. Figure 1 shows the conceptual design analyzed in this study, in which the reservoirs are constructed from aluminum. For the simulation, turbulence k-ε models and heat transfer in fluid are used respectively for profiles of velocity and temperature using the data reported in table 1. Results are agree with experimental data. Table 3 Performance of photovoltaic/thermal system 2 Radiation incident 900 W/m Loss efficiency 0,11% for K Reflected energy 30% Energy to heat 40% Electrical efficiency 11% Total efficiency 61% Temperature 323 K Area 100 m2 Electric power 102 W/m2 Thermal power 360 W/m2 Figure 4 Conceptual PVT design analyzed in this study Figure 6 Temperature profile of refrigeration fluid Figure 5 Velocity profile of refrigeration fluid inside inside the photovoltaic/thermal system the photovoltaic/thermal system Reference [1] Ibrahim, A.; Othman, M.; Ruslan, M.H.; Mat, S.; Sopian, K.; Renew Sustain Energy Rev. 2011,15, 352–65. 107 | P44 SUPPRESSION OF OPTICAL BANDGAP RECOMBINATION IN PHOTODEPOSITED NiOX-COATED HEMATITE ELECTRODES FOR WATER SPLITTING APPLICATION F. Malara,*,a F. Fabbri,b M. Marelli,a V. Dal Santo,a R. Psaro,a A. Naldonia a CNR-Istituto di Scienze e Tecnologie Molecolari, c/o Dipartimento di Chimica, Via Venezian, 2, 20133 Milano, ITALY b IMEM-CNR, Parco Area delle Scienze 37/A, 43100 Parma, Italy e-mail: [email protected] Photocatalytic splitting of water has attracted extensive attention since the discovery of the Fujishima and Honda effect,1 providing a route for storing solar energy in the form of chemical bonds in hydrogen and oxygen. Intensive studies are dedicated to develop materials for oxygen evolution, that represent the bottleneck of the process, and hematite (α-Fe2O3) is one of the most promising.2,3 Nevertheless, superficial defects considerably reduce the photoelectrochemical conversion efficiency of the electrodes.4,5 We report the effects of photodeposition and elettrodeposition of Ni cocatalyst on hematite electrodes. We found that both techniques produce an increase of water splitting efficiency with respect to bare hematite, but photodeposition produces results that are more effective: the enhancement of maximum photocurrent at 1.23V vs. RHE was of 47%, while the current onset anticipates of 150 mV. Cyclic voltammetry in dark shows that these two deposition techniques produce two different phases of Ni hydroxides and a different superficial distribution. In particular, we have a strong reduction of the charge transfer resistance at electrode/electrolyte interface in the case of photodeposition. By cathodoluminescence (CL) spectroscopy, we observed that nickel deposition induces changes in the intensity of the spectral distribution of the CL emission, as compared with the bare material. Both depositions lead a reduction of the ligand to metal charge transition (LMCT), but photodeposition induces a selective surface passivation of the hematite electrodes that further reduces the optical band gap recombination. References [1] Fujishima and K. Honda, Nature, 1972, 238, 37 [2] J. A. Seabold and K. S. Choi, Chem. Mater., 2011, 23, 1105 [3] S. H. Baeck, K. S. Choi, T. F. Jaramillo, G. D. Stucky and E. W. McFarland, Adv. Mater., 2003, 15, 1269 . [4] B. Klahr, S. Gimenez, F. Fabregat-Santiago, T. Hamann, and J. Bisquert, J. Am. Chem. Soc., 2012, 134 (9), 4294–4302 [5] M. Barroso, S. R. Pendlebury, A. J. Cowanc and J. R. Durrant, Chem. Sci., 2013, 4 P45 | 108 A NOVEL ENVIRONMENTALLY FRIENDLY 3-V Na-ION CELL Jessica Manzi, Sergio Brutti Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano 10, 85100 Potenza, Italy e-mail: [email protected] Thanks to the high abundance and low cost of sodium, as well as its very suitable redox potential (i.e. 2.71 V vs NHE) which is only 0.3 V above that of lithium, sodium-ion batteries are considered a promising alternative to the current lithium-ion systems [1]. Our attention is focused on environmentally friendly electrode materials such as cobaltfree cathodes and carbonaceous anodes from biomasses. In particular we report here our results concerning the scalable synthesis of β-NaMnO2 –type cathode materials [2] and a hard carbon materials [3]. Materials have been characterized by synchrotron XRD, FT-IR and Raman spectroscopy, SEM, TEM, XPS and then tested in metallic sodium half cells. Excellent performances have been obtained in repeated galvanostatic cycling at low and high current rates. Finally, by combining the β-NaMnO2 based cathode and the hard-carbon based anode a full sodium-ion cell (anode limited configuration) has been assembled and galvanostatically tested: an average specific capacity of 180 mAhg-1 at 3.3 V has been achieved. References [1] D. Kundu, E. Talaie, V. Duffort, and L. F. Nazar, “The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage Angewandte,” no. 150, pp. 3431–3448, 2015. [2] J. Billaud, R. J. Clément, A. R. Armstrong, J. Canales-Vázquez, P. Rozier, C. P. Grey, and P. G. Bruce, “β-NaMnO2 : A High-Performance Cathode for Sodium-Ion Batteries,” J. Am. Chem. Soc., vol. 136, no. 49, pp. 17243–17248, 2014. [3] D. a. Stevens and J. R. Dahn, “02 High Capacity Anode Materials for Rechargeable Sodium-Ion Batteries,” J. Electrochem. Soc., vol. 147, no. 4, p. 1271, 2000. 109 | P46 COMPARATIVE LCA OF A BIPV APPLICATION: AMORPHOUS SILICON VS DYE SENSITIZED SOLAR WINDOWS Simone Maranghi,a Maria Laura Parisi,a Adalgisa Sinicropi, a Riccardo Basosi * a University of Siena, Via A. Moro 2, Siena, Italy e-mail: [email protected] Among the emerging photovoltaics, the dye sensitized solar cells (DSSC) [1] have attracted much interest for their potential as an economically and environmentally viable alternative to traditional devices. Even though efficiency, stability and lifetime need to increase yet to be industrially competitive, the research and development activity on DSSC has achieved noteworthy improvements in order to find the proper set of materials while much fewer records have been reached in setting the best architectures for dye sensitized solar module (DSSM) [2]. The development of DSSM, like all new and innovative technologies, requires an overall evaluation of the product’s environmental impacts and benefits and Life Cycle Assessment (LCA) is one of the most powerful methods for sustainability assessment. This methodology has demonstrated to be pivotal in understanding the environmental dynamics, benefits and drawbacks associated with DSSC technology showing it has the potential to become a strong contributor toward the solar energy conversion market, with respect to other thin-film photovoltaic technologies [3]. In this context, the DSSC technology could represent one of the best options in the Building Integration Photovoltaic (BIPV) market area. In fact, thanks to their particular configuration, DSSMs can be manufactured with optical transparency and coloring characteristics suitable to be used as an alternative to traditional passive glass window. The market of 'smart photovoltaic windows' has rapidly increased in the very last years thanks to the development of solutions proposed by several companies already active in the photovoltaic sector. Nowadays, the main thin-film PV technology used for the manufacturing of this type of window is based on the amorphous silicon (a-Si). In this study we present the preliminary results of a comparative LCA between a dye sensitized solar window and an amorphous silicon one for BIPV application. References [1] Grätzel M, O'Regan B. 1991. A Low-Cost, High Efficiency Solar Cell Based on DyeSensitized Colloidal TiO Films. Nature 353:737-740. [2] Fakharuddin A., Jose R., Brown T. M., Fabregat-Santiago F, Bisquert J. 2014. A perspective on the production of dye sensitized solar modules. Energy and Environmental Science 7: 3952-3981 [3] Parisi M. L., Maranghi S., Basosi R. 2014. The evolution of the dye sensitized solar cells from Grätzel prototype to up-scaled solar applications: A life cycle assessment approach. Renewable and Sustainable Energy Reviews 39:124-138. P47 | 110 Cu2MnSnS4: AN ALTERNATIVE CHALCOGENIDE TO PUSH THE PV ON TW-SCALE Stefano Marchionna,a Federico Cernuschi,a Alessia Le Donne,b Simona Binetti,b Maurizio Acciarri,b Marco Merlini,c a RSE-Spa Ricerca sul Sistema Energetico Via Rubattino 54, Milano, Italy. Material Science dept. Milano-Bicocca University, Via Cozzi 53, Milano,Italy. c Earth scince dept. Milano University , Via Botticelli, 23, Milano, Italy. b e-mail: [email protected], The mitigation of the forecast increase of CO2 atmospheric concentrations to levels that might prevent anthropogenic alterations of the world climate requires tens of terawatts (TW) of renewable energy resources. The combined energy production potential of all known non-solar renewable resources seems insufficient to meet these targets. Consequently, over the next decades the development of efficient photovoltaic (PV) absorbers based on earth-abundant materials is expected to fill the gap, enabling TWscale production of solar electricity. Thin-film (TF) PV technologies, based on low-cost and high-throughput deposition process, represent a possible route to reach the TW-scale. In particular, TF solar cells based on direct band gap chalcogenides, such as CdTe and Cu(In,Ga)Se2 (CIGSe) show PV-record efficiencies compatible with the best Si-bases solar devices. However, these materials contain rare and expensive metals (e.g. In ≈0.049 ppm, Se ≈0.05ppm and Te ≈0.005ppm), not allowing a cost-effective large-scale production. However, alternative copper-based quaternary chalcogenide semiconductors based on earth-abundant elements (e.g: Cu2ZnSn(S,Se)4 (CZTS)) have been recently proposed as valid potential candidates to move PV in the TW-Scale. More in general, CZTS is a member of a more extended family of chalcogenides ( Cu2M(II)M(IV)S4 (M(II) = Mn, Fe, Co, Ni, Cd, Hg; M(IV)= Si, Ge, Sn)) that has never been systematically studied. Furthermore, multi-crystalline TFs of these compounds based on earth-abundant elements, have been never grown and tested in PV devices. The aims of this work has been focused on the growth and characterization of Cu2MnSnS4 (CMTS) TF for PV applications. To better control the final composition of CMTS-based TF, a two-steps process (evaporation in vacuum of the metallic precursors and a successive heat treatment in Sulphur vapor) has been used and optimized. Molybdenum-coated (1µm) soda-lime glass has been used as substrates in this work. For this preliminary study, the effects of the most critical growth parameters on TF quality (homogeneity and stoichiometry) has been investigate. In particular, both the order of the metallic precursors in the evaporated multilayer and the sulphurization temperature have been optimized to grow continuous CMTS TF. Three different orders of the metallic precursors (Cu/Sn/Mn) and different heating ramps for the sulphurization process have been compared. EDX, XRD and Raman measurements have been collected to identify other possible secondary phases. Also these data has been also used to feedback the growth parameters. An high absorption coefficient (5x104), and suitable direct band (≈ 1.26 eV) for FV applications has been observed for an homogenous CMTS TF. 111 | P48 LiBH4/ZrCoH3 DOPING EFFECT ON THE H2 STORAGE KINETICS OF LiNH2-MgH2 COMPLEX HYDRIDE Alessio Masala, Jenny G. Vitillo, Silvia Bordiga, Marcello Baricco Chemistry Department, NIS and INSTM reference Centres, University of Torino, Via Quarello 15/A,10135 Torino e-mail: [email protected] Metal and complex hydrides are considered a promising class of materials for H2 storage thanks to their high gravimetric and volumetric capacities.[1] The development of systems that can guarantee high uptakes of H2 within temperatures and pressures of interest, in a cheap and green way, led to the study of LiNH2-MgH2 complex hydride and the effect of LiBH4/ZrCoH3 doping on its H2 kinetic of absorption.[2,3] After performing kinetic and equilibrium (PCI) measurements on the mixture at different temperatures, a combination of techniques such as P-XRD and IR spectroscopy (in ATR mode) applied to the hydrogenated doped material at 170 °C and different H2 coverage (from 0 to 100 bar), allowed to understand the role of ZrCoH3 which acts as pulverizing agent for some components of the mixture (MgH2) avoiding agglomerations and promoting the H2 absorption kinetics. For what concern LiBH4, its behavior within the mixture was explored by means of the same techniques: its presence promotes the formation (already at 100 °C) of a low-melting ionic liquid (Li4BH4(NH2)3) that helps in the homogenization of the mixture and so allows the metathesis reaction between LiNH2 and MgH2 to start at lower temperatures (from 200 °C to 150 °C). This work, financed by the SSH2S EU project,[4] brought to the implementation of LiNH2-MgH2-LiBH4-ZrCoH3 mixture in a fuel tank-FC integrated system ready for real applications. a b Fig.1 a) P-XRD patterns of LiNH2-MgH2-LiBH4-ZrCoH3 mixture hydrogenated from 0 to 100 bar, at 170 °C. The presence of low-melting ionic liquid Li4BH4(NH2)3 was identified from this study. b) Kinetic desorption (1.4 bar) and absorption (90 bar) curves for the complex hydride mixture at 170 °C, for three cycles. References [1] W. Grochala, P. P. Edwards, Chem. Rev,. 2004, 104, 1283–1315. [2] A. Zuttel, P. Wegner, S. Rentsch, P. Sudan, P. Mauron, C. Emmenegger, J. Power Sources, 2003, 118, 1–7. [3] X. Zhang, Z. Li, F. Lv, H. Li, J. Mi, S. Wang, X. Liu and L. Jiang, Int. J. Hydrog. Energy, 2010, 35, 7809–7814. [4] http://www.ssh2s.eu/index.php P49 | 112 CONCENTRATION OF VINASSE BY PHYSICOCHEMICAL PROCESSES, USING FERRIC SULFATE P. Sica1; A. S. Baptista1; C. L. Aguiar1; R. S. Carvalho1; M. Silverio1; R. P. Calegari1; F. C. Tonoli1; A. Trevizan1; M. Outeiro1; E. M. Carvalho1; J. P. Neto2 1 2 College of Agriculture “Luiz de Queiroz”, Padua Dias Avenue, Piracicaba, Brazil. Tractebel Energia, Paschoal Apóstolo Pística, Florianópolis, Brazil. e-mail: [email protected] Increasingly mankind has been seeking alternative sources to replace fossil fuels. In many parts of the world, ethanol appears as a renewable energy option and Brazil is not different. In 2014, it produced about 28.6 billion liters of ethanol from sugarcane. However, in this production process wastes are generated, such as vinasse. The vinasse has a high polluting power and fertilizer and is generated in large volumes. For every liter of ethanol produced, are generated 10-18 liters of vinasse. Aiming to take advantage of the minerals present in its composition, the vinasse is widely used as a fertilizer, in a process called fertigation. However, due to the high water content (97%) and power pollutant, management, handling and transportation of this waste to the field are expensive and can cause environmental impacts. So it is necessary to study alternatives for the treatment of such waste. Among the alternatives, the concentration of solids by means of physical and chemical processes noteworthy. For these reasons, the objective of this experiment was to verify the efficiency of ferric sulfate in solids concentration of vinasse in different concentrations and settling times. It was used natural vinasse with turbidity of 771NTU, pH 4.66 and 1.39% total solids. This vinasse was divided into 9 treatments: 0ppm; 200ppm; 500 ppm of ferric sulfate, decanting for 1 h; 4h; 24. Each treatment was conducted with 3 replications in 1 L beakers, and the work volume of 300mL. After the settling period, the supernatant was centrifuged at 4,000 rpm for 10 minutes. The results in the reduction of turbidity (%) are shown in Table 1: Treatment 200ppm 4h 200ppm 24h 500ppm 24h 500ppm 4h 200ppm 1h 0ppm 24h 500ppm 1h 0ppm 4h 0ppm 1h Turbidity reduction (%) 81.85 a 81.51 a 80.77 a 80.21 a 77.62 b 77.36 b 76.79 b 75.94 b 63.65 c Table 1: Analysis of the settling time effect and concentration of ferric sulfate by Tukey test at 1%. As can be seen in Table 1, the Tukey test was verified that the treatments with 200 and 500ppm and settling time of 4h and 24h showed a significant difference compared to the other treatments. Achieving a reduction of up to 81.85% in the final turbidity. Furthermore, it is possible to highlight the treatments 200ppm and 500ppm for 4 hours in solids concentration at which 51% and 59% solids were concentrated during the process, respectively. Whereas the other treatments had a mean concentration of about 30% solids. Therefore, statistically, it is clear that the addition and ferric sulfate at 200 and 500 ppm is effective in reducing the turbidity of vinasse and solids concentration. Reference [1] FARIA, A. A. A. Concentração da Vinhaça e Reaproveitamento da Água - IV Semana de Tecnologia do Curso de Biocombustíveis da Faculdade de Tecnologia de Jaboticabal, 2011 113 | P50 CONCENTRATION OF VINASSE BY PHYSICOCHEMICAL PROCESSES USING ALUMINUM SULFATE. P. Sica1; A. S. Baptista1; C. L. Aguiar1; R. S. Carvalho1; M. Silverio1; R. P. Calegari1; F. C. Tonoli1; A. Trevizan1; M. Outeiro1; E. M. Carvalho1; J. P. Neto2 1 2 College of Agriculture “Luiz de Queiroz”, Padua Dias Avenue, Piracicaba, Brazil. Tractebel Energia, Paschoal Apóstolo Pística, Florianópolis, Brazil. e-mail: [email protected] Brazil is the largest producer of ethanol from sugarcane. In the distillation for the production of sugarcane ethanol is generated a by-product with low pH and high content of organic matter and minerals, vinasse. On average, for each liter of ethanol produced, are generated 10-18 liters of vinasse, therefore, esteemed that the Brazil annually generates about 300 billion liters of this waste. The vinasse is composed by 97% of water, which makes the transportation from the plant to the field expensive, due to the high volume. Therefore, an alternative to the treatment of this byproduct is the concentration of the solids, making it a source of water to the plant and reducing the value of the handling and application in the field. Because of these reasons, the objective of this project was to verify the efficiency of physical and chemical processes in solids concentration of this waste, using lime and aluminum sulfate as flocculants agents. . For this, was used natural vinasse with 781NTU turbidity, pH 4.33, conductivity 133mV and 1.93 % total solids. In order to reduce the content of suspended solids, vinasse was centrifuged at 4,000 rpm for 10 minutes, reducing the turbidity at 74% and total solids from 1.93% to 1.67 %. The centrifuged vinasse was divided into 6 treatments with 4 repetitions each: T1) no reagent at room temperature; T2) without reagent to 70° C; T3) aluminum sulfate 100ppm at room temperature; T4) 100ppm aluminum sulphate , at 70° C ; T5) aluminum sulfate 200ppm at room temperature; T6) aluminum sulfate 200ppm , to 70°. The beakers containing vinasse 400mL were shaken and left to settling for 12 hours. Subsequently, the supernatant was siphoned and filtered on a filter containing activated charcoal, coarse sand, fine sand, fine gravel, coarse gravel and cotton. After filtration, the following parameters were analyzed for each treatment: turbidity, pH, conductivity, total solids. Figure 1 shows the vinasse in nature, treatment T1 and T5 treatment filtrates: Figure 1: vinasse in natura, filtered T1 and filtered T5. After filtration process was observed in all treatments reduced turbidity and high total solids, in addition to increasing the pH.The T5 treatment, in which the pH was adjusted to 7.6 with lime and then added 200 ppm of aluminum sulfate at room temperature, the turbidity was reduced to 25NTU (96.80 %), total solids 0.15% and the pH and conductivity were 7.04 and -9, respectively. Therefore, we conclude that the physical chemical process solids concentration of vinasse by centrifugation, flocculation, sedimentation and filtration was efficient, generating a product with low turbidity and pH close to 7.0. However, more studies are needed to verify the feasibility of implanting this in a sugarcane mill. References [1] FARIA, A. A. A. Concentração da Vinhaça e Reaproveitamento da Água - IV Semana de Tecnologia do Curso de Biocombustíveis da Faculdade de Tecnologia de Jaboticabal, 2011 P51 | 114 PRODUCTION OF BIOENERGY FROM BYPRODUCT OF SUGARCANE MILL P. Sica1; A. S. Baptista1; C. L. Aguiar1, K. C. Das2; J. P. Neto3 *,c 1 College of Agriculture “Luiz de Queiroz”, Padua Dias Avenue, Piracicaba, Brazil. University of Georgia, 597 Brooks Drive, Athens-Ga, USA 3 Tractebel Energia, Paschoal Apóstolo Pística, Florianópolis, Brazil. 2 e-mail: [email protected] The rational use of natural resources should be adopted in all sectors of the economy, in the sugarcane chain is no different. In this sense, the vinasse, one of by-product of ethanol production process, deserves attention because it has a high polluting power and fertilizer and is composed of 97% water. One way to take advantage of this rich material is performing anaerobic digestion. This process is the reduction of organic matter, pH increasing, producing methane, with mineral bit changing characteristics of the effluent. Methane can be used to supply a dryer yeast plant, used as animal feed supplement, and generate electricity. The effluent may be subjected to a purification process, recovering the water and resulting in a concentrated biofertilizer. The recovered water can be used at various stages of the manufacturing process, such as soaking, during juice extraction, steam generation in the boiler among others. The digestion occured in a 4,5 litres UASB reactor, during 135 days. In the period of 105 days, the methanogenesis process was highly efficient, when was possible to verify the average pH of the effluent during the methanogenesis was 7.13 ranging from 6.9 7.6. The average reduction of COD was 80.8% (initial COD= 30 gL-1). For each liter of digested vinasse, it was produced 4,7 liters of CH4. During the last 30 days, the reactor was fed with a more concentrated vinasse. During this period was possible to verify the average pH of the effluent during methanogenesis was 7.01, with little variation between 6 9 and 7.1. The reduction of COD was 80.1%, ranging from 72.82 to 92.23%. The average methane production was 8.13 liters of CH4 per liter of medium in fermentation, with range from 5.53 to 10.54 liters of CH4 per liter substrate (vinasse). The pH of the effluent and the reduced COD percentage kept virtually unchanged when increased in 37.3% the concentration of COD in the UASB reactor. However, the las period was highlighted in efficiency of methane production, increasing by about 32% the generation of this gas by COD unit reduced when compared to the previous period. Increased efficiency in the anaerobic digestion process is even more visible when comparing the potential of thermal energy per cubic meter of ethanol produced, which increased from 564 Mcal per cubic meter of ethanol to 710.4 Mcal per cubic meter of ethanol. Besides reducing the volume of vinasse produced, this by-product, more concentrated, was shown to have high potential for methane production when subjected to anaerobic digestion. However, more studies are still needed to verify to what extent the increase in the concentration of COD is beneficial to the process in question and what the maximum potential for methane production from vinasse in a UASB reactor. References [1] LETTINGA, G. (1996), Advanced anaerobic wastewater in the near future, in Anaerobic Treatment. A grown up technology, Papers of the IAWQ-NVA Conference on Advanced Wastewater Treatment (Aquatech 1996), Amsterdam, The Netherlands, 24-32 115 | P52 SCREENING AND STUDY OF LOW-COST OER PHOTOELECTROCATALYSTS BY SCANNING ELECTROCHEMICAL MICROSCOPY (SECM) Sara Morandi,a Alberto Naldoni,b Cristina Locatelli,a Francesco Malara,c Vladimiro Dal Santo,c Alberto Vertova,a,b Sandra Rondinini,a,b Alessandro Minguzzia a Università degli Studi di Milano – Department of Chemistry; INSTM Milano Unit; Via Golgi 19 – 20133 Milano – Italy b associate to C.N.R. – I.S.T.M., Via Golgi 19 – 20133 Milano – Italy c CNR – Istituto di Scienze e Tecnologie Molecolari, Via Golgi 19, 20133 Milan, Italy e-mail: [email protected] The production of H2 from sunlight by photoelectrochemical water splitting represents one of the most attractive strategies for energy conversion. In the last years a lot of effort has been devoted to the study of different semiconductor/electrocatalyst combinations. In particular, recent studies highlighted the ability of some electrocatalysts used as overlayers in inducing modification of the semiconductor electron density [1] or in storing the photogenerated holes, thus decreasing the probability of charge recombination [2,3]. This greatly extends the possible candidates for photoelectrocatalysts and requires new efficient screening methods. In this context, scanning electrochemical microscopy (SECM) is an optimal tool for the screening of electrocatalysts, e.g. for oxygen reduction [4] and evolution [5] reactions, and photocatalysts [6]. In this communication we will show our most recent results obtained using SECM to study both semiconductors and overlayers. The semiconductor chosen for its low-cost, stability and favorable bands position is hematite (α-Fe2O3), in the form of nanoplatelets [7]. Study and screening of the deposited materials were done both using a white light LED through an optic fiber or by detecting the reaction products using an microelectrode. In particular, the latter was used in the substrate generation/tip collection (SG/TC) mode or adopting a double pulse method [8], which consists in pulsing the substrate potential between a rest and a OER potential to reduce the overlapping of different spots oxygen profiles. At the same time, the tip is kept close to the spot under investigation and collects the generated oxygen. References [1] Barroso, M.; Mesa, C. A.; Pendlebury, S. R.; Cowana, A. J.; Hisatomi, T.; Sivula, K.; Grätzel, M.; Klug, D. R.; Durrant J. R. PNAS 2012, 109, 15640. [2] Badia-Bou, L.; Mas-Marza, E.; Rodenas P.; Barea, E. M.; Fabregat-Santiago, F.; Gimenez, S.; Peris, E.; Bisquert, J. J. Phys. Chem. C 2011,117, 3826. [3] Lin, F.; Boettcher, S.W.; Nature Materials 2014, 13, 81. [4] Fernández, J. L.; Walsh, D. A.; Bard, A. J. J. Am. Chem. Soc. 2005, 127, 357. [5] Minguzzi, A.; Alpuche-Aviles, M. A.; Rodríguez-López, J.; Rondinini, S.; Bard, A. J. Anal. Chem. 2008, 80,4055. [6] Lee, J.; Ye, H.; Pan, S.; Bard, A. J. Anal. Chem. 2008, 80, 7445. [7] Marelli, M.; Naldoni, A.; Minguzzi, A.; Allieta, M.; Virgili, T.; Scavia, G.; Recchia, S; Psaro, R.; Dal Santo, V. ACS Appl. Mater. Interfaces 2014, 6, 11997. [8] Minguzzi, A.; Battistel, D.; Rodríguez-López, J.; Vertova, A.; Rondinini, S.; Bard, A. J.; Daniele, S. J. Phys. Chem. C, 2015, 119, 2941. P53 | 116 NEW INSIGHTS TOWARDS AGING RESISTANT LITHIUM POLYMER BATTERIES FOR WIDE TEMPERATURE APPLICATIONS Jijeesh R. Naira, Luca Porcarellia, Federico Bellaa, Rongying Linb, Sebastien Fantinib, Giovanna Marescac, Margherita Morenoc, Giovanni B. Appetecchic, Claudio Gerbaldia a GAME Lab, CHENERGY Group, Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy b Solvionic SA, Chemin de la Loge, FR-31078 Toulouse, France c ENEA, Agency for New Technologies, Energy and Sustainable Economic Development, UTRINN-IFC, via Anguillarese 301, Rome, Italy e-mail: [email protected] A wide interest is mounting in the field of polymer electrolytes, due to their application in energy efficient devices such as rechargeable batteries, photo-electrochemical cells, electrochromic devices, fuel cells and super capacitors. Polymer electrolytes exhibit unique advantages such as mechanical integrity, wide variety of fabrication methods in desirable size and shape, possibility to fabricate an intimate electrode/electrolyte interface and adapt to a lightweight, leak proof construction, safety and economic packaging structure. In this communication, we offer a summary of our recent and most interesting results regarding the synthesis, physico-chemical and electrochemical characterization of solid polymer electrolytes (SPEs) based on different monomers/oligomers (methacrylic and/or ethylene oxide based) with specific amounts of lithium salt, plasticizers and/or fillers. Profoundly ion conducting (σ > 10–4 S cm–1 at 20 °C), electrochemically stable (> 5 V vs. Li), self-standing, robust and tack-free SPEs are successfully prepared via a rapid and easily up-scalable process including a light induced photo-polymerization step and/or by thermal polymerization. The crosslinking produced by UV irradiation allows the incorporation of higher amounts of tetraglyme and/or RTIL (e.g., imidazolium, pyrrolidinium) with lithium salt (based on TFSI– anion), leading to a material with remarkable morphological characteristics in terms of homogeneity and mechanical abusability under highly stressful conditions. The lab-scale Li-polymer cells assembled show stable charge/discharge characteristics without any capacity fading at C/5 current regime (> 130 mAh g–1 in LiFePO4/Li configuration and > 150 mAh g–1 in TiO2/Li configuration @ 20 °C exploiting tetraglyme). Noteworthy, the ability to resist the lithium dendrite nucleation and growth is demonstrated by means of galvanostatic polarization studies. The overall performance of the SPEs postulates the possibility of effective implementation in the next generation of safe, durable and high energy density secondary all-solid Li-ion as well as Li-metal polymer batteries working at ambient and/or sub-ambient temperatures. Acknowledgements MARS-EV project has received funding from the European Union Seventh Framework Program (FP7/2007-2013) under grant agreement n° 609201. Lithops batteries S.r.l. is acknowledged for providing the LiFePO4 electrodes. 117 | P54 SILICON-DRIVEN MORPHOLOGY, STRUCTURE, AND WATER SPLITTING ACTIVITY IN HEMATITE NANOSTRUCTURES Francesco Malaraa, Mattia Allietab, Marcello Marellia, Saveria Santangeloc, Salvatore Patane'd, Claudia Triolod, Rinaldo Psaroa, Vladimiro Dal Santoa, Alberto Naldonia a CNR – Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, 20133, Milano, Italy. Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy c Dipartimento di Ingegneria Civile, dell’Energia, dell’Ambiente e dei Materiali (DICEAM), Università“Mediterranea” di Reggio Calabria, Loc. Feo di Vito, 89122 Reggio Calabria, Italy d Dipartimento di Scienze matematiche e Informatiche, Scienze Fisiche e Scienze della Terra, Università di Messina, Viale F. Stagno d’Alcontres, 31 - 98166 Messina, Italy b e-mail: [email protected] Hematite (α-Fe2O3) is a promising photoanode in solar photoelectrochemical (PEC) water splitting with a theoretical solar-to-fuel conversion of 14-17%, which corresponds to a photocurrent of 11–14 mA cm−2. [1-3] However, α-Fe2O3 performances are limited by its low conductivity and short holes diffusion length (only few nm). Among the methods used to improve its photocurrent, Si-doping has driven intense research delivering α-Fe2O3 photoanodes with record efficiency of 4 mA/cm2. [1] Besides the increased conductivity, the understanding of the effects produced by the introduction of tetravalent dopants such as Si4+ (or Ti4+) on structural and PEC properties remains elusive. [4,5] In this contribution, we analyzed the morphological, structural, and PEC activity changes due to the systematic insertion of Si (1, 5, 10, 15, 20%) in α-Fe2O3 nanostructures prepared through a solvothermal route. SEM and TEM analysis revealed that pure α-Fe2O3 crystallized as hollow nanorods. The introduction of Si induced a transition to Si-α-Fe2O3 with acicular shape. Raman, synchrotron radiation powder diffraction (SRPD), XPS and EDX/STEM measurements were employed to detect the structural changes due to Si inclusion in α-Fe2O3 lattice. As the amount of Si in the α-Fe2O3 increased, the atomic % of O and Fe2+ augmented. This pointed out to a doping mechanism where the additional charge due to the substitution of Fe3+ with Si4+ was compensated both by Fe valence reduction and interstitial O. The variation of the atomic composition of α-Fe2O3 structure was reflected by increased structural disorder and trend of atomic distances. Finally, α-Fe2O3 powders were tested in a traditional three-electrodes PEC cell under AM1.5G illumination observing an optimum of 1% Si-doping. Through impedance measurements the charge transfer resistance and donor density were extracted and correlated to Si-content, structure and morphology of α-Fe2O3 nanostructures. References [1] Warren, S. C.; Voïtchovsky, K.; Dotan, H.; Leroy, C. M.; Cornuz, M.; Stellacci, F.; Hébert, C.; Rothschild, A.; Grätzel, M. Nat. Mater. 2013, 12, 842. [2] Marelli, M.; Naldoni, A.; Minguzzi, A.; et Al. Appl. Mater. Interfaces 2014, 6, 11997. [3] Malara, F.; Minguzzi, A.; Marelli, M.; Morandi, S.; Psaro, R.; Dal Santo, V.; Naldoni., A. ACS Catal. 2015, 5, 5292. [4] Kay, A.; Cesar, I.; Grätzel. M. J. Am. Chem. Soc. 2006, 128, 15714. [5] Monllor-Satoca, D.; Bärtsch, M.; Fàbrega, C. et Al. Energy Environ. Sci. 2015, 8, 3242. P55 | 118 NEW PHOTOACTIVE MATERIALS BASED ON DOPED ZrO2 M.C. Paganini*, Chiara Gionco, Elio Giamello a Dipartimento di Chimica, Università di Torino, via Giuria 7, 10125, Torino e-mail: [email protected], Among the semiconductors employed in photocatalytic reactions, transition metal oxides play a paramount role due to their qualities in term of stability in various media often accompanied by low or reasonable cost. The search for innovative materials in these field is oriented to select systems having a suitable electronic structure capable of harvesting solar light (which means essentially visible light) and excellent potential to perform the desired redox process. This is practically impossible to be found in a unique system. Solid materials with large band gap values correspond, in principle, to good reduction and oxidative potentials but inevitably, to perform the charge separation, need high energy photons (UV light, scarcely present in solar irradiation at the earth surface). On the other hand semiconductors with smaller band gap value, compatible with visible light absorption, may have unsatisfactory potentials for both reduction and oxidation. A possibility to overcome this drawback consists in modifying a semiconductor with relatively large band gap in order to make possible the absorption of visible light. This has been done intensely in the case of titanium dioxide, following more than an approach including doping with non metal atoms [1]. In the present contribution we intend to analyze the modification of the light absorption mechanism induced by engineering the band gap of ZrO2 and show how using low energy photons it is somehow possible to convey electrons in the conduction band generating holes in the valence band in spite of the relatively large band gap value of the oxide (5eV). In our study we synthesized ZrO2 based mixed oxides with different lanthanide oxides [2] and with different processes. Encouraging results have been obtained especially with the sample Ce-ZrO2 having lower ceria loading (0.5%). Recent results on La-ZrO2 and Pr-ZrO2 open new perspective towards new photocatalytic materials. Both reduction and oxidation photoactivity of these samples have been verified through paramagnetic resonance (EPR). The photoformation of both electrons (reacting with oxygen and producing superoxide anions) and holes necessary to entail photocatalytic processes has been demonstrated irradiating with visible light (λ>420nm). References [1] Livraghi, S.; Paganini, M.C.; Giamello, E.; Selloni, A.; Di Valentin, C.; Pacchioni, G.; J. Am. Chem. Soc. 2006,128, 15666. [2] Gionco C.; Paganini M.C.; Giamello E.; Burgess R.; Di Valentin C.; Pacchioni G.; J Phys.Chem.Lett. 2014, 5, 447. 119 | P56 EFFECTS OF Ni/Co DOPING ON THE PROPERTIES OF LiFeαNiβCoγPO4 CATHODES FOR LITHIUM BATTERIES Gioele Pagot,a Federico Bertasi,b Graeme Nawn,b Enrico Negro,b Giuseppe Pace,b,c Stefano Polizzi,d Vito Di Noto*,a a Department of Industrial Engineering University of Padova, via Gradenigo 6/a, Padova, Italy. Department of Chemistry University of Padova, via F. Marzolo 1, Padova, Italy. c CNR-IENI, Via F. Marzolo 1, Padova, Italy. d Department of Molecular Sciences and Nanosystems and Centre for Electron Microscopy “G.Stevanato” Università Ca’ Foscari Venezia, Via Torino 155/B, Venezia-Mestre , Italy. b e-mail: [email protected]. Nowadays, rapid development in portable electronics, load leveling/peak shaving for the power grid and electric automotive, requires significant progress in high voltage and high capacity storage systems.1 Lithium batteries are, to date, the most promising systems that can sustain this demand;2 they have high specific energy, high efficiency and a long lifespan.3 Lithium cobalt oxide (LiCoO2) based cathode materials currently dominate the market,4 however, due to a low working potential (3.0 – 4.0 V vs. Li) and a high cost and toxicity, there is broad scope for the development of new cathodic materials.5 Lithium-transition metal-phosphates (LiMPO4, M=Co, Fe, Mn or Ni) show very good performance: their olivine structure, consisting of a 2D framework of crossed tunnels, allows the insertion and de-insertion of lithium ions during the discharge/charge of the battery.6, 7 In this work we describe the synthesis and characterization of a new family of high voltage cathodic materials based on lithium-transition metal mixture-phosphates of iron, nickel and cobalt (taking advantage of all the positive electrochemical attributes of each element presents in the structure).8 Five materials have been produced, varying the Ni/Co molar ratio; the effect of different degrees of Co and Ni doping have been thoroughly studied: we evaluated the stoichiometry, thermal stability, morphology and size distribution, and the structure. Electrochemical properties have been exhaustively characterized with different techniques. Indeed, the proposed materials are good cathodic candidates for the development of high voltage lithium batteries: the best of our materials LFNCP0.61 showed a specific capacity and a specific energy of 125 mAh·g-1 and 560 mWh·g-1, respectively. References [1] Armand, M.; Tarascon, J.M. Nature 2008, 451, 652. [2] Di Noto, V.; Zawodzinski, T.A.; Herring, A.M.; Giffin, G.A.; Negro, E.; Lavina, S. Int. J. Hydrogen Energy 2012, 37, 6120. [3] Scrosati, B.; Garche, J. J. Power Sources 2010, 195, 2419. [4] Zaghib, K.; Mauger, A.; Groult, H.; Goodenough, J.B.; Julien, C.M. Mater. 2013, 6, 1028. [5] Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C.M. J. Power Sources 2012, 219, 36. [6] Bramnik, N.N.; Bramnik, K.G.; Buhrmester, T.; Baehtz, C.; Ehrenberg, H.; Fuess, H. J. Solid State Electrochem. 2004, 8, 558. [7] Padhi, A.K.; Nanjundaswamy, K.S.; Goodenough, J.B. J. Electrochem. Soc. 1997, 144, 1188. [8] Pagot, G.; Bertasi, F.; Nawn, G.; Negro, E.; Carraro, G.; Barreca, D.; Maccato, C.; Polizzi, S.; Di Noto, V. Adv. Funct. Mater. 2015, 25, 4032. P57 | 120 DINUCLEAR TRICARBONYL RE(I) COMPLEXES: NEW EFFICIENT ELECTROCATALYTIC SYSTEMS FOR CO2 REDUCTION Elsa Quartapelle Procopio,a Monica Panigati,*,a Alessandro Boni,b Pierluigi Mercandelli,a Giovanni Valenti,*,b Francesco Paolucci b a Dipartimento di Chimica, Università degli Studi di Milano,Via Golgi 19, 20133 Milano, Italy. Dipartimento di Chimica ‘‘G. Ciamician’’, Università degli Studi di Bologna, via F. Selmi 2, 40126 Bologna, Italy. b e-mail: [email protected] The increasing amount of carbon dioxide in the atmosphere and a steady climb in global fuel demand, make the catalytic conversion of CO2 to liquid fuels a critical goal for the scientific community. As a matter of fact the research in this field has rapidly grown in the past few years [1-2]. The challenges presented are great, but the potential rewards are enormous. In this context we report here the activity of dinuclear Re(I) complexes of general formula [Re2(µ-X)2(CO)6(µ-N∩N)] (X = Cl, Br, I, N∩N = pyridazine, see Figure 1) [3] towards the electrocatalytic reduction of carbon dioxide. The electrochemical characterizations are carried out in highly aprotic conditions and the comparison with the analogues mononuclear Re(I) complexes, [Re(bpy)(CO)3(Cl)] points out the outstanding performances of these dinuclear Re(I) complexes. In particular, complexes containing electron-donating alkyl groups have displayed better electrocatalytic perfomances than those containing the unsubstituted pyridazines. This reflects the higher strength of the diazine binding to the metal core of the former complexes. Moreover the activity follows the trend Cl<Br<I in line with the electronegativity of the halogen. This indicates an essential role of the ancillary ligand in the mechanism of CO2 coordination and subsequent reduction. Figure 1: Molecular structures of the dinuclear Re(I) complexes used as catalysts and cyclic voltammograms of 0.5 mM [Re2(µ-X)2(CO)6(µ-diazine)], 80 mM TBAPF6 in CH3CN, and CO2 saturated solution References [1] Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. Chem. Soc. Rev., 2014, 43, 631 [2] (a) Fujita, E. Coord. Chem. Rev. 1999, 185-186, 373; (b) Benson, E. E.; Kubiak, C. P.; Sathrum, A. J.; Smieja, J. M. Chem. Soc. Rev., 2009, 38, 89–99 [3] Valenti, G.; Panigati, M.; Boni, A.; D’Alfonso, G.; Paolucci, F.; Prodi, L. Inorg. Chim. Acta 2014, 417, 270. 121 | P58 A NEW SEMI-SOLID, FLOW Li/O2 BATTERY Irene Ruggeri, Catia Arbizzani, Francesca Soavi* Alma Mater Studiorum - Università di Bologna, Department of Chemistry “Ciamician” Via Giacomo Selmi 2, 40126-Bologna, Italy e-mail: [email protected] Redox flow batteries (RFBs ) and Li-ion batteries (LIBs) are energy storage/conversion systems that play a key role for high penetration of intermittent and decentralized renewable energy sources and of electric vehicles Many research efforts have been devoting to increase energy and power of both RFBs and lithium batteries with attention to costs, safety and reliability. As it concerns RFBs, the main strategies are the use of i) organic electrolytes to increase cell voltage above 2 V and to widen temperature operation, ii) solid metal anodes and iii) O2 (air) based catholytes to reduce volume and weight, iv) semi-solid anolyte and/or catholyte to circumvent the active material solubility issues of conventional RFBs. Combination of these different approaches have proliferated many RFB configurations [1]. As it concerns the lithium batteries, the Li/O2 are considered the next generation for their significant higher energy than “conventional” Li-ion cells [2,3]. Here, we report a radically new battery concept, a non-aqueous semi-solid flow Li/O2 battery which combines the high energy density of Li/O2 battery with the flexible and scalable architecture of RFBs [4,5]. The cell operates with a flowable O2-satured catholyte, which is pumped through the battery, having lithium metal as anode. The catholyte is a suspension of high surface area carbon in oxygen-saturated non-aqueous electrolyte. ORR takes place on the semisolid electroactive particles dispersed in the catholyte, avoiding the electrode passivation, enhancing the capacity and, in turn, the generate energy. Exceptionally high capacity is achieved at voltages >2.6 V vs Li/Li+ and high discharge rates (> 2.5 mA/cm2) of interest for practical applications. The results of the galvanostatic tests at different current densities are here reported and discussed. Aknowledgements Alma Mater Studiorum –Università di Bologna is acknowledged for financial support (RFO, Ricerca Fondamentale Orientata). References [1] Soloveichik, G. L. Chem. Rev. 2015, 115, 11533. [2] Bruce, G. B.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J.-M.; Nat Mater 2012, 11, 19. [3] Grande, L.; Paillard, E.; Hassoun, J.; Park, J.-B.; Lee, Y.-J.; Sun, Y.-K.; Passerini, S.; Scrosati, B. Adv. Mater. 2014, 27, 784. [4] Soavi, F; Arbizzani, C.; Ruggeri, I. Patent application (102015000040796). [5] Ruggeri, I.; Arbizzani, C.; Soavi, F. En. Env. Sci., submitted. P59 | 122 NOVEL ORGANIC DYES IN PHOTOELECTROCHEMICAL SYSTEMS Federica Sabuzi, Emanuela Gatto, Mariano Venanzi, Barbara Floris, Valeria Conte, Pierluca Galloni* Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata, Via della ricerca scientifica, 00133, Roma, Italia e-mail: [email protected] KuQuinones (KuQs) belong to a new class of pentacyclic quinoid compounds, synthesized for the first time few years ago in our research group [1]. KuQuinone derivatives are characterized by a broad absorption spectrum in the visible region, due to the extended electronic conjugation over the five rings and a low reduction potential compared to simpler quinoid compounds. These features suggested the potential application of these novel compounds as dyes in photoelectrochemical devices. In this regard, promising results in terms of photocurrent generation have been obtained using KuQs-functionalized ITO as working electrode and triethanolamine (TEOA) as electron donor species [2]. A stable and high anodic photocurrent signal was detected, according to the mechanism proposed in Figure 1. However, efficiencies seem to be affected by the low absorbance of the photoactive material due to the lower surface area of ITO electrode with respect to other nanoporous surfaces. R O O O HO Figure 1: Left: KuQuinones general structure. Right: Proposed mechanism for the anodic photocurrent generation in presence of TEOA. In this contribution we report preliminary results obtained using KuQuinone derivatives anchored on nanoporous surfaces, in order to test their ability to act as sensitive material also in dye sensitized solar cells. References [1] Coletti, A.; Lentini, S.; Conte, V.; Floris, B.; Bortolini, O.; Sforza, F.; Grepioni, F.; Galloni, P. J. Org. Chem. 2012, 77, 6873. [2] Sabuzi, F.; Armuzza, V.; Conte, V.; Floris, B.; Venanzi, M.; Galloni, P:; Gatto, E. submitted. 123 | P60 HIGHLY POROUS ELECTROSPUN HEMATITE FIBRES FOR PHOTOELECTROCHEMICAL WATER SPLITTING Saveria Santangelo,*,a Patrizia Frontera,a Fabiola Pantò,b Alberto Naldoni,c Francesco Malara,c Marcello Marelli,c Vladimiro Dal Santo,c Salvatore Patané,d Claudia Triolo,d Pierluigi Antonuccia a Dipartimento di Ingegneria Civile, dell’Energia, dell’Ambiente e dei Materiali (DICEAM), Università “Mediterranea”, Reggio Calabria, Italy b Dipartimento di Ingegneria dell’Informazione, delle Infrastrutture e dell’Energia Sostenibile (DIIES), Università “Mediterranea”, Reggio Calabria, Italy c Istituto di Scienze e Tecnologie Molecolari (ISTM), Consiglio Nazionale delle Ricerche (CNR), Milano, Italy d Dipartimento di Scienze Matematiche e Informatiche, Scienze Fisiche e Scienze della Terra (DSMISFST), Università di Messina, Messina, Italy e-mail: [email protected] Solar energy conversion for hydrogen production via photo-induced water splitting represents one of the most promising approaches to the development of clean energy sources [1]. This contribution deals with the synthesis, characterisation and testing, as photo-anodes for photo-electrochemical activity (PEC), of hematite (α-Fe2O3) fibres. Synthesis is carried out by means by electro-spinning (ES), a very competitive technique for the preparation of 1-dimensional high surface area materials [2,3]. Fe2O3 fibres were synthesised by using DMF, PAN and iron(II) acetate as solvent, polymer and oxide precursor, respectively. ES was carried out at 20°C (Fig.1a) for 2 or 4 min on fluorine-doped tin oxide (FTO) substrates (Fig.1b). Fibres calcined in air at 600°C (~170 nm thick) resulted to be highly-porous (Fig.1c) and constituted by interconnected grains (Fig.1d). They were tested without any pre-conditioning. PEC performance was investigated, in 1M NaOH solution, by means of a 3-cell system. Ag/AgCl and Pt electrodes were used as reference and counter electrode, respectively; fibrous Fe2O3 films on FTO/glass substrate acted as working electrode. The thinner film (2 min spinning) exhibited very poor activity, as its thickness was too low. Conversely, the PEC activity of the thicker film (4 min spinning) was higher: at 1.23 V vs. RHE (reversible hydrogen electrode) the photocurrent value is 1 µA/cm2. The fast reduction of the current value when the light is switched off suggests the occurrence of strong recombination processes. However, charge injection efficiency could be increased by optimising the hematite film adhesion to the FTO/glass subs123rate. Fig. 1. (a) ES set-up; (b) calcined Fe2O3/FTO film; (c) SEM and (d) TEM images of the Fe2O3 fibres. References [1] A. Fujishima, K. Honda, Nature 238, 37, 1972. [2] S. Shen, J. Mater. Res. 29, 29, 2014 [3] G. Faggio et al, J. Raman Spectr. 43, 761, 2012. P61 | 124 INTERMEDIATE TEMPERATURE SOFC FED BY BIOGAS: EXTERNAL REFORMER DEVELOPMENT Caterina Sarno1, Igor Luisetto2, Simonetta Tuti2, Silvia Licoccia1, Elisabetta Di Bartolomeo1 1 Department of Chemical Science and Technologies, University of Rome Tor Vergata, Via della Ricerca Scientifica 1, 00133 Rome, Italy 2 Department of Sciences, University of Rome “Roma Tre”, Via della Vasca Navale 79, Rome, Italy email: [email protected] Solid oxide fuel cells working at intermediate temperature (IT-SOFCs) represent a valid alternative technology to convert chemical energy into electrical energy with high efficiency. The cells, working at a temperature range of ≈ 500–850°C, make possible to use hydrocarbon as fuel. In this contest the biogas, produced by anaerobic fermentation of organic biomass, might be employed as a renewable source, for the reforming of methane because it contains CO2 as reforming agent. The CO2 reforming of CH4 (eq.1), otherwise known as dry reforming (DRM), is a strongly endothermic process that is operated at high temperatures (generally above 800°C) to achieve suitable CH4 and CO2 conversions. 0 CH 4 + CO2 → 2 H 2 + 2CO (1) ∆H 298K = 247kJmol −1 This work is focused on the development of an external reformer of methane using Nibased structured and unstructured catalysts. Nickel is so far the most active catalyst for the DRM, but also highly prone to carbon formation, because, together with the ability to activate the C-H bond, Ni has an high affinity to carbon. The Ni particle size has a strong effect on the carbon tolerance of the catalyst, therefore, the stabilization of small Ni nanoparticles at high temperatures is a promising way for the lifetime increase [1,2]. The catalysts were prepared by wet impregnation of active phase (10wt.% Ni) on γAl2O3 or Ru(0.05 wt.%)/γ-Al2O3 and wash coating deposition of the carrier on cordierite monoliths. Ni was homogeneously distributed along the monolith channels forming species in low (Ni-α) and strong (Ni-β) interaction with the −Αλ2Ο3. The samples were characterized by XRD, FE-SEM, H2-TPR, BET techniques and the catalytic activity for DRM was evaluated at 800°C during time on stream (TOS) at different GHSV. Preliminary catalytic tests showed that Ni particles, obtained by reduction of Ni-α species, were active for the DRM reaction with low carbon formation, whereas catalysts with large amount of Ni-β deactivated rapidly during TOS without carbon formation. The Ni–Ru catalysts showed, initially, low catalytic activity for the presence of chlorides coming from RuCl3 used for the synthesis and not completely eliminated during calcination. Indeed Cl-adatoms supress the chemisorption of CH4 and its dehydrogenation on metallic surface, being the rate determining step for the DRM reaction [3, 4]. After several washes with H2O, the Cl-free catalyst showed the most performing behaviour with very low amount of coke. Moreover, the comparison between structured and unstructured catalyst underlined the advantages of structured catalysts over conventional packed bed reactors such as: increased mass and heat transfer, lower pressure drop, larger surface to-volume ratio and compact reactor design. References [1] K. Mette, S. Kühl, H. Düdder, K. Kähler, A. Tarasov, M. Muhler, M. Behrens, ChemCatChem 6 (2014) 100-104. [2] Z. Li, L. Mo, Y. Kathiraser, S. Kawi, ACS Catalysis 4 (2014) 1526-1536. [3] I. Luisetto, S. Tuti, C. Battocchio, S. Lo Mastro, A. Sodo, Appl. Catal. A 500 (2015) 12–22. [4] Y. J. Bang, S. Park, S. J. Han, J. Yoo, J. Song, J.H. Choi, K. Kang, I. K. Song, Appl. Catal. B: Environmental 180 (2016) 179–188. 125 | P62 IN SILICO DESIGN OF NEW SENSITIZERS FOR TYPE II DSSC Adalgisa Sinicropi*,a Maria Laura Parisi,a Gianna Reginato,b Lorenzo Zani, b Massimo Calamante,b Alessandro Mordini,b Riccardo Basosi,a Maurizio Taddeia a Università degli Studi di Siena, Dipartimento di Biotecnologie, Chimica e Farmacia, Via A. Moro 2, 53100 Siena, Italy; bCNR-Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy, e-mail: [email protected] In the last two decades fully organic molecules, mainly based on a D(Donor)-π(spacer)A(Acceptor/Anchoring) structure, have been designed and tested as promising dyes for dye sensitized solar cells (DSSCs) [1]. These dyes, most of which featuring a carboxyl group as anchor, are sensitizers for type I DSSCs where the electron injection pathway is indirect, i.e. the electron injection into the conduction band (CB) of TiO2 (photoanode) follows the excitation of the dye (Scheme, left). More recently, catecholbased (Cat) dyes have attracted much attention for their capability to exhibit broad photoabsorption dye-to-TiO2 charge transfer (DTCT) bands in the longer wavelength region upon binding to TiO2. Cat dyes are the light-harvesting molecules for type II DSSCs where the electron injection pathway is direct, i.e. the electron is injected by photoexcitation of the DTCT bands (Scheme, middle). In addition to the improved absorption capabilities, the direct mechanism overcomes the restriction regarding the energy of the LUMO that in type I DSSCs should be higher than the CB of the oxide. Unfortunately, up to now Cat type II DSSCs have shown very low efficiency, about 2% [2], compared to that of type I, which instead have shown efficiencies exceeding 10%. Nevertheless, so far very few efforts have been made to develop more efficient Cat dyes for DSSCs and increase our knowledge about the direct mechanism. With this aim we embarked in the in silico design of novel and potentially more efficient Cat type II DSSCs using the methods of density functional theory. In particular, we investigated the effect of strongly electron-donating or electron-withdrawing substituents (Scheme, right) on the DTCT properties of the newly designed Cat dyes. The results of this in silico investigation are presented. References [1] Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, 595; Dessì, A.; Calamante, M.; Mordini, A.; Peruzzini, M.; Sinicropi, A.; Basosi, R.; Fabrizi de Biani, F.; Taddei, M.; Colonna, D.; Di Carlo, A.; Reginato, G.; Zani, L. Chem. Commun. 2014, 50, 13952. [2] Ooyama, Y.; Kanda, M.; Uenaka, K.; Ohshita, J. Chem. Phys. Chem. 2015, 16, 3049. P63 | 126 PERFORMANCE OF PEM ELECTROLYSIS MEAs BASED ON ADVANCED ELECTROCATALYSTS AND MEMBRANE Stefania Siracusano,a Vincenzo Baglio,a Eddy Moukheiber,b Luca Merlo,b Antonino Salvatore Arico’,a a b CNR-ITAE, Via Salita S. Lucia sopra Contesse 5 – 98126 Messina, Italy Solvay Specialty Polymers Italy SpA, viale Lombardia, 20 20021 – Bollate, Italy e-mail: [email protected] An Ir0.7Ru0.3Ox nanosized anode electrocatalyst was coupled to an Aquivion short-side chain perfluoro-sulfonic acid membrane (120 µm; EW: 870 g/eq) for operation in a PEM electrolyser. A conventional carbon supported Pt catalyst was used as cathode. An excellent performance, of 4 A·cm-2 at 1.9 V at 90°C, was achieved for this electrolyser configuration in the presence of a moderate noble metal loading (1.5 mg·cm-2 Ir + Ru; 0.5 mg·cm-2 Pt). The interface of IrRuOx with Aquivion provided a 10% enhancement in performance compared to an equivalent interface with a Nafion membrane of similar thickness but characterized by a larger equivalent weight (EW: 1100 g/eq). The enhanced performance essentially derived from a decrease of polarization resistance. This appeared to be due to better interface characteristics between the electrodes and Aquivion® ionomer giving rise to an increased catalyst utilization. Whereas, no significant change in Tafel slope and activation energy was recorded indicating a similar reaction mechanism. Acknowledgement. The authors acknowledge the financial support of the EU through the FCH JU Electrohypem Project. “The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2010-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement Electrohypem n° 300081.” References [1] S. Siracusano, N. Van Dijk, E. Payne-Johnson, V. Baglio, A.S. Aricò, Applied Catalysis B: Environmental, 2015, 164, 488-495. [2] A.S. Aricò, S. Siracusano, N. Briguglio, V. Baglio, A. Di Blasi, V. Antonucci, Journal of Applied Electrochemistry, 2013, 43, 107-118. [3] S. Siracusano, V. Baglio, E. Moukheiber, L. Merlo, A.S. Aricò, Int. J. Hydrogen Energy, 2015, 40, I4430-I4435. 127 | P64 POLY(CYANOVINYLENE PHENYLENE-CO-THIOPHENE)S FOR POLYMER SOLAR CELLS Francesco Tassinari,a Francesca Parenti,a Francesco Paolo Di Nicola,b Barbara Ballarin,b Massimiliano Lanzi,b Emanuela Libertini,*,a Adele Mucci.*,a a Università di Modena e Reggio Emilia, Dipartimento di Scienze Chimiche e Geologiche, Via Campi 103, 41125 Modena, Italy. b Università di Bologna, Dipartimento di Chimica Industriale "Toso Montanari" Viale Risorgimento 4, 40134 Bologna, Italy. e-mail: [email protected] Conjugated polymers like poly(p-phenylene vinylene) (PPV) are mainly investigated for their sustainable energy applications such as thin film solar cells [1,2] and light emitting devices [3]. However, the optical and electronic properties of these polymers are strongly connected to the structure that they have in the solid state, especially as thin films. The rules governing these structure-property relationships are still not completely clear. Figure 2: General structure of the CN-PPV-T polymers used in this study. Using a Knoevenagel poly-condensation reaction, we synthetized three different poly(cyanovinylene phenylene-co-thiophene)s (CN-PPV-T) (Fig.1), slightly changing the structure of the thiophene comonomer from one to the other (Fig.2), in order to study the effect that these changes would have on the efficiency of photovoltaic devices built using these polymers. Figure 3: The thiophene comonomers used in the study. The presence of the alkylsulfanyl group in the side-chain was chosen to improve the stability and efficiency of the CN-PPV-T polymers available in the literature [4,5]. References [1] N. S. Sariciftci, L. Smilowitz, A. J. Heeger, F. Wudl; Science, 1992, 258, 5087, 1474–1476. [2] S. E. Shaheen, C. J. Brabec, N. S. Sariciftci, F. Padinger, T. Fromherz, J. C. Hummelen; Appl. Phys. Lett., 2001, 78, 6, 841–843. [3] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes; Nature, 1990, 347, 6293, 539–541. [4] P. Morvillo, F. Parenti, R. Diana, C. Fontanesi, A. Mucci, F. Tassinari, L. Schenetti; Solar Energy Materials and Solar Cells, 2012, 104, 45–52. [5] A. Mucci, F. Parenti, L. Schenetti; Macromol. Rapid Comm., 2003, 24, 9, 547–550. P65 | 128 EFFECT OF THE PREPARATION METHOD ON THE ELECTROCHEMICAL PROPERTIES OF PYROPHOSPHATEBASED CATHODES FOR RECHARGEABLE Na-ION BATTERIES Cristina Tealdi,a Monica Ricci,a Chiara Ferrara,a Giovanna Bruni,a Eliana Quartarone,a Piercarlo Mustarellia a Department of Chemistry, University of Pavia and INSTM, Viale Taramelli 16, 27100 Pavia, Italy e-mail: [email protected] Improvements in rechargeable batteries performances attract a great deal of attention, both in the portable and stationary applications market. The search for technological advancements justifies an increasing demand for materials optimization in terms of faster charge/discharge and capacity retention over prolonged usage. In addition, metalions alternative to Li for use in room-temperature rechargeable batteries are currently under intense investigation and, in this context, Na-ion batteries materials, in particular cathode materials, are the subject of a growing research interest. [1,2] Among the cathode materials currently proposed for use in Na-ion batteries, one of the most interesting is the family of sodium metal pyrophosphates of general formula Na2MP2O7 (M = Co, Cu, Fe, Mn).[3] Pyrophosphate-based cathodes are normally prepared through a solid state reaction process, possibly followed by reduction of the particle size and carbon coating. [4] In this study Na2FeP2O7 was prepared through three different synthetic procedures: conventional solid state reaction, glucose-assisted solid state reaction and wetchemistry (citrate) method. The materials were characterized for what concerns their structural, morphological and electrochemical process through X-ray diffraction, scanning electron microscopy, cyclic voltammetry, charge/discharge curves. The electrochemical results are compared and discussed in terms of morphological considerations. It is generally observed that higher C rates bring along poorer cycling performances and capacity retention. Interestingly, the results show that, especially for high C rates, the electrochemical behavior of the compound is highly dependent upon the preparation method. This is consistent with the fact that different preparation methods modulate the morphological properties and the intrinsic carbon coating of the material. References [1] Yabuuchi N.; Kubota, K.; Dahbi M.; Komaba S. Chem. Rev. 2014, 114, 11636. [2] Kim S.-W.; Seo D.-H.; Ma X.; Ceder G.; Kang K. Adv. Energy Mater. 2012, 2, 710. [3] Barpanda P.; Nishimura S.-I.; Yamada A. Adv. Energy Mater. 2012, 2, 841. [4] Barpanda P.; Ye T.; Nishimura S.; Chung S.-C.; Yamada Y.; Okubo M.; Zhou H; Yamada A. Electrochem. Commun. 2012, 24, 116. 129 | P66 Pd-Au CATALYST FOR THE HYDROGENATION OF LEVULINIC ACID TO γ−VALEROLACTONE γ− AT MILD CONDITION Maria Luisa Testa,*,a Valeria La Parola a and Anna Maria Venezia a a CNR-ISMN Palermo, via Ugo La Malfa 153, 90146 – Palermo, Italy e-mail: [email protected] It is well known that, nowadays, for a sustainable production of fuels, one of the most important approaches is the valorization of biomass residue. From the acid treatment of lignocellulosic materials, platform chemical levulinic acid (LA) can be easily obtained. [1] LA can be further converted into many valuable chemicals. The catalytic hydrogenation of this acid leads to the formation of γ-valerolactone (GVL) [2]. Recently, the effect of different supports, silica HMS and Ti doped silica HMS, on the catalytic performance of mono (Pd) and bimetallic (Pd-Au, Pd-Re) catalysts, containing 2 wt% of each metal, for the hydrogenation of levulinic acid in water was studied. [3] In that case the strong reaction condition (T=160°C and P=150 bar) induced a synergic effect of Au and Ti with the consequent formation of a PdTi alloy responsible of the good performance of the catalyst. In this work, the effect of different support (SBA and Ti doped SBA) and milder reaction condition on the catalytic performance of Pd and Pd-Au catalysts for the hydrogenation of levulinic acid is investigated. The catalytic behavior of the materials is evaluated in terms of conversion of the starting levulinic acid and selectivity to γvalerolactone. The surface and structural properties of the catalysts are investigated by means of X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) performed on fresh and spent materials. References [1] T. Werpy, G. Petersen, A. Aden, J. Bozell, J. Holladay, J. White, A. Manheim, D. C. Elliott, L. Lasure, S. Jones, TopValue Added Chemicals From Biomass, Department of Energy, Washington 1, 2004 [2] W. Wright , R. Palkovits R. ChemSusChem 5 (2012) 1657-1667 [3] M. L. Testa, L. Corbel-Demailly, V. La Parola, A.M. Venezia, C. Pinel Catalysis Today, 2015, 257, 291-296 P67 | 130 WO3 NANOROLLS SELF-ASSEMBLED AS THIN FILMS BY HYDROTHERMAL SYNTHESIS: A VERSATILE MATERIAL FOR ELECTRO-OPTICAL APPLICATIONS. Svetoslava Vankova,*,a Simone Zanarini,a Julia Amici,a Nerino Penazzi,a Silvia Bodoardoa a DISAT, Polytechnic of Turin, corso Duca degli Abruzzi 24, Turin, Italy e-mail: [email protected]* We report a Novel WO3 nanostructure that we call nanorolls [1]. The nanocrystals were obtained as self-assembled thin film directly on a transparent conductive substrate. The preparation conditions were mild: the use of HCl was avoided resulting in an ecofriendly hydrothermal method with time of reaction substantially shorter than the previously reported HT methods. Interestingly the length of the fibrous structures can be tuned by varying precursor (polyvinyl alcohol, PVA) chain length. Characterization by FESEM and HR-TEM microscopy put in evidence that WO3 nanocrystals are made of rolled nanoflakes with a telescope-like appearance in their final portion. Considering its nano-porosity, electrochemical accessibility, good adhesion to the underlying substrate and the possible presence of nanocavities between the rolled layers, the new material is very versatile from the point of view of possible applications. Nanorolls in fact, are promising as electrochromic devices, water photo-splitting cells, Li-ion batteries and nano-templated filters for short wavelength UV radiation. FESEM pictures showing the effect of PVA chain length on the sub-structure morphology of a nanoroll fiber. PVA molecular weight is increasing from left to right. Acknowledgments: This research has been carried out in the context of the FP7European Project “RESSEEPE” (grant agreement no. 609377). References [1] Vankova, S.; Zanarini S.; Amici J.; Camara F.; Arletti R.; Bodoardo, S.; Penazzi N. Nanoscale, 2015, 7, 717. 131 | P68 COMMERCIAL ALUMINUM ALLOY AS ANODE FOR Li-ION BATTERIES Svetoslava Vankova,*,a Roberto Doglione,b Nerino Penazzi,a Silvia Bodoardoa a DISAT, Polytechnic of Turin, corso Duca degli Abruzzi 24, Turin, Italy Inter University National Consortium Materials Science and Tecnology (INSTM), via G. Giusti 9, 50121 Firenze, Italy b e-mail: [email protected]* The use of light metals and alloys as an anode material for Li-ion cells [1, 2] is an interesting possible alternative to graphite to maintain light weight and increase safety. Al anodes have been investigated because of their low potential versus Li, high theoretical capacity [3], electric conductivity, abundance, recyclability. The first new results on the behavior of the commercial lithium and copper containing aluminum alloy 2090-T8 as Li-ion cell anode are reported. Following a standardized procedure, the commercial alloy was prepared as 50 µm sized powder and used as anodic active material. Polypropylene three-electrode T-cells were assembled by contacting in sequence the working electrode (Al or 2090-T8 coated powder), a 1.0 M LiPF6 in a 1:1 w/w% mixture of ethylene carbonate and diethyl carbonate electrolyte soaked on a Whatman ® GF/A separator and a lithium foil counter electrode. A comparison was carried out between the electrochemical behavior of pure aluminum and the 2090-T8 alloy. Galvanostatic cycling tests (see figure), carried out at a current density of 100 mAg-1, show that the alloy electrode has a higher capacity which fades much more slowly than pure Al. The coulombic efficiency of the 2090-T8 alloy (~80%) also is higher than the one of pure Al anode (~53%). The experiments suggest that in the alloy new phases appear during formation capable of stabilizing the electrode structure during cycling. References [1] Hudak, N.; Huber, D. J. Electrochem. Soc., 2012, 159, A688 [2] Zhang, L.; Song, X.; Wang F.; Hu Q.; Sun, Z.; Yang S.; Wang L.; Sun, S. J. Solid State Electrochem., 2012, 16, 2159 [3] Lindsay, M.; Wang, G.; Liu H.; J. Power Sources, 2003, 119-121, 8 P69 | 132 TRIARYLAMINE-BASED HYDRIDO-CARBOXYLATE RHENIUM(I) COMPLEXES AS PHOTOSENSITIZERS FOR DYESENSITIZED SOLAR CELLS Lorenzo Veronesea, Elsa Quartapelle,a Pierluigi Mercandellia, Thomas Moehlc, Monica Panigati,a Anders Hagfeldtb a Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy Laboratory of Photomolecular Science (LSPM), ISIC, École Polytechnique Fédérale de Lausanne, CH1015, Lausanne, Switzerland c Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057, Zürich, Switzerland b e-mail: [email protected] The use of a dinuclear rhenium complex, containing a triarylamine (TPA) moiety, as sensitizer in dye-sensitized solar cells has been recently investigated [1]. The complex (1 in the Chart), which belongs to the recently reported family of dinuclear rhenium complexes [2], is endowed with a 4-pyridazine-carboxylic acid, acting both as anchoring group on the TiO2 surface and as electron withdrawing moiety, and by two anionic ancillary ligand, one of them being an hydride. In order to increase the extinction coefficient of the sensitizer, a more conjugated TPA linker, containing bulky butoxyphenyl substituents, has been introduced. This ligand is one of the most common triarylamine-based metal-free organic sensitizers [3], in which the carboxylic group has been exploited for the coordination to the organometallic scaffold, obtaining complex 2. Finally, the use of a different diazine ligand has been considered, affording complex 3. The cell performances of the three rhenium-based dyes have been investigated both using iodide/triiodide and cobalt redox couples as electrolytes, and platinum or carbon as counter electrodes respectively. Results show an improvement of photocurrent generation and power conversion efficiency up to 3.5% obtained with complex 3. 1 2 3 Fig. 1. J–V characteristics of the solar cells containing the three dyes: solid line represents cells with I-/I3electrolyte and Pt as counter electrode; dashed line cells with Co2+/3+ electrolyte and C as counter electrode. Acknowledgements The authors thank the Italian Ministero dell’Istruzione, Università e Ricerca, for the financial support (PRIN-2012A4Z2RY) References [1] L. Veronese, E. Quartapelle, F. De Rossi, P. Mercandelli, T. Brown, P. Mussini, G. D'Alfonso, M. Panigati, manuscript submitted [2] M. Panigati, M. Mauro, D. Donghi, P, Mercandelli, P. Mussini, L. De Cola, G. D’Alfonso, Coord. Chem. Rev. 2012, 256, 1621-1643 [3] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev., 2010, 110, 6595– 6663; Chem. 2011, 50, 4825. 23 1 133 | P70 ANODIC MATERIALS FOR LITHIUM-ION BATTERIES: TIO2rGO COMPOSITES FOR HIGHPOWER APPLICATIONS. Daniele Versaci,a Marco Minella,b Claudio Minero,b Carlotta Francia,a Silvia Bodoardo,a Nerino Penazzi a a Department of Applied Science and Technology, Politecnico di Torino, c.so Duca degli Abruzzi 24, 10129 Torino, Italy b Department of Chemistry and NIS Inter-departmental Centre, University of Torino, via P. Giuria 5, Torino,10125, Italy e-mail: [email protected] The market of Lithium-ion batteries (LIBs) is constantly increasing [1]. LIBs initially found applications in electronics and portable devices; however, they are actually extending their presence to the automotive field, and are replacing the NiMH technology especially considering hybrid and micro-hybrid electrical vehicles [2]. We report here the results regarding the preparation and testing of titanium dioxide/reduced graphene oxide (TiO2-rGO) composites used as anodic material in LIBs for high-power applications. TiO2-rGO hybrids were synthesized at different loadings of the carbonaceous phase and tested as anode materials in Lithium-ion cells. Particular attention has been paid to the feasibility of industrial scale-up. GO was synthesized from graphite [3], adsorbed onto commercial TiO2 anatase and reduced to obtain rGO with chemical, photocatalytic and hydrothermal procedures [4]. The synthesized materials were fully characterized using a multi-technique approach, consisting of structural-morphological analysis and electrochemical testing techniques. TiO2-rGO obtained with the first two procedures showed good cycle stability, high capacity and impressive rate capability, conversely the sample reduced by hydrothermal procedure discloses low capacity and scarce cycling stability. The photocatalytic reduction was also applied on pre-formed electrodes reaching the goal of a further simplification of the anode production. The promising performances, from the point of view of the specific capacity, were correlated with the true graphene oxide reduction and with the maintenance of the 2D geometry of the final graphenic structure observed for the TiO2-rGO hybrids obtained by both the chemical and photocatalytic reduction procedure. Moreover the excellent electrochemical properties at high C-rate (i.e. until 40C), show that these materials are promising candidate as anode in LIB especially for power application. References [1] Schmid, R.; Pillot, C. Review on Electrochemical Storage Materials 2014, 1597, 3. [2] Horiba, T. Lithium-Ion Battery Systems, Proc. IEEE 2014, 102, 939. [3] Hummers, W.S.; Offeman, R.E. J. Am. Chem. Soc. 1958, 80, 1339. [4] Minella, M.; Demontis, M.; Sarro, M.; Sordello, F.; Calza, P.; Minero, C. J. Mater Sci. 2015, 50, 2399. P71 | 134 EFFICIENCY ENHANCEMENT BY CATION EFFECT IN DSSC WITH PAN BASED GEL POLIMER ELECTROLYTES Ottavia Bettucci,a,b,c Massimo Calamante,b,c Alessandro Mordini,b,c Lorenzo Zani,b Gianna Reginato,b Murizio Peruzzini,b T.M.W.J. Bandara,d Valeria Saavedra,d Maurizio Furlani,d Bengt Erik Mellanderd a Dipartimento di Biotecnologie Chimica e Farmacia, Università degli Studi di Siena, via A. Moro 2, 53100 Siena, Italy. b Istituto di Chimica dei composti organometallici (CNR-ICCOM), via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy. c Dipartimento di Chimica “U. Shiff” Università degli Studi di Firenze, via della Lastruccia 13, 50019 Sesto Fiorentino, Italy. d Department of Applied Physics, Chalmers University of Technology, Kemivagen 9, 412 96 Göteborg, Sweden. e-mail: [email protected] The electrolyte is one of most important components of a Dye-sensitizer solar cells (DSSC) since it can determine the efficiency and the stability of a cell. Lately the research activity is focused on gel electrolytes instead of the liquid ones, because they should increase the long-term stability and the efficiency[1] of the devices. The conduction of iodide ions in gel polymer electrolytes and the performance of a DSSC, containing such an electrolyte, can be enhanced by incorporating different salts. In this work the samples were made with PAN, ethylene carbonate (EC), propylene carbonate (PC), salt, and I2. The purpose of the first part of this work have been the evaluation of the effects of cation size in the enhancement of the efficiency of a commercial dye (D35) preparing 5 different samples containing 5 different salts (LiI, NaI, KI, RbI, CsI). The second part of this work is focused on the evaluation of the mixed cation effect using 6 samples containing different amounts of RbI:LiI. In this case we have used another dye (DF15) synthesized in our research group[2]. The variation of conductivity with salts concentration has been discussed in order to understand the mechanism of iodide ion conductivity in this system. We also used transient spectroscopy to understand how the regeneration and recombination process change using different salts in the composition of the electrolytes. References [1] Bandara, T.M.W.J.; Jayasundera, W.J.M.J.S.R.; Fernado, H. D. N. S.; Dissanayakea, M.A.K.L.; De Silva, L. A. A.; Fernando, P. S. L.; Furlani, M.; Mellander, B. E. J Appl Electrochem, 2014, 44, 917 [2] Franchi, D.; Calamante, M.; Reginato, G.; Zani, L.; Peruzzini, M.; Taddei, M.; Fabrizi de Biani, F.; Basosi, R.; Sinicropi, A.; Colonna, D.; Di Carlo, A.; Mordini, A. Tetrahedron, 2014, 70, 6285. 135 | P72 DESIGN AND SYNTHESIS OF PHOTOSENSITIZERS WITH ALKOXYSILANE ANCHORING GROUPS FOR NEW GENERATION SOLAR CELLS Matteo Bessi,a,b Marco Monini,b Massimo Calamante,b,c Alessandro Mordini,b,c Adalgisa Sinicropi,a Mariangela Di Donato,c,d Alessandro Iagatti,c,d Paolo Foggi,c,d Lorenzo Zanib, Gianna Reginato*,b a Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via A. Moro 2, 53100 Siena, Italy. b Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy. c Dipartimento di Chimica ‘‘U. Schiff’’, Università degli Studi di Firenze, Via della Lastruccia 13, 50019 Sesto Fiorentino, Italy. d European Laboratory for Non Linear Spectroscopy (LENS), Università degli Studi di Firenze, Via Nello Carrara 1, 50019 Sesto Fiorentino, Italy. e-mail: [email protected] As one of the most promising classes of third-generation PV technologies, dyesensitized solar cells (DSSC) have been the subject of constant attention in recent years thanks to the enhancement in their efficiency and stability.1 Metal-free D-π-A dyes (characterized by donor (D) and acceptor (A) moieties joined by a conjugated unit) are especially interesting, since their particular architecture allows a fine adjustment of their photo- and electrochemical properties.2 First, we modified the structure of already known dye DF15 by introducing two alkoxysilane anchoring groups characterized by different spacers (1, propyl vs. 2, phenyl). This silicon-based moiety has been recently awarded to be one of the most stable and high-performing anchoring units for DSSC3. Then, we altered the dye conjugate unit by replacing the central thiophene ring with a more electronrich ProDOT moiety, keeping the trialkoxyphenylsilyl anchor (3), with the aim to improve the dye light harvesting properties. The corresponding cyanoacrylic acid dye was also prepared for comparison (4). Finally, we analyzed the interfacial charge transfer processes taking place between the dyes and a nanocrystalline semiconductor (TiO2), by means of UV-Vis and IR transient absorption spectroscopy. The results obtained with the various anchoring groups were compared in order to study the different dynamics occurring in each case. References [1] Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, 6595 [2] Ooyama, Y.; Harima, Y. ChemPhysChem. 2012, 13, 4032 [3] Kakiage, K.; Aoyama, Y.; Yano, T.; Otsuka, T.; Kyomen, T.; Unno, M.; Hanaya, M. Chem. Commun. 2014, 50, 6379 P73 | 136 DRIVING THE SELECTIVITY OF ELECTROCHEMICAL CO2 REDUCTION TO FORMIC ACID: SYNERGIC EFFECTS IN A CBASED HETEROSTRUCTURE Boni A.a, Valenti G. a, Montini T.b, Fornasiero P.b Prato M.,b Paolucci F.a a Università di Bologna, Dipartimento di Chimica “G. Ciamician” , Bologa , Italy Università di Trieste, Dipartimento di Scienze Chimiche e Farmaceutiche, Center of Excellence of Nanostructured Material (CENMAT), Trieste, Italy b e-mail: [email protected], CO2 concentration in the atmosphere increased from 320 ppm in the early 60’s, to more than 400 ppm in 2014, with an exponential trend never observed before. It is thus not surprisingly that recently a lot of efforts were focused in the research and improvement of new/existing materials, catalysts, methods, and technologies, able to capture and to convert CO2 in useful products.1 The design of new electrocatalysts that reduce CO2 in a selective and efficient fashion is a key step for future exploitation of this technology. In this work we present how the combination of different building blocks in a single nanostructure might be a good strategy to achieve a good selectivity in the CO2 reduction process. Combining the unique physico-chemical properties of functionalized f-MWCNTs and nanocrystalline cerium dioxide (CeO2) we revealed faradaic efficiency for formic acid production as high as 55% at an overpotential as low as 0.02V in acid solutions. These performances have been possible by the in-operando formation of partially reduced ceria (CeO2-X), responsible of an increased CO2 adsorption2 and a more efficient electron transfer at the surface. The fundamental role of MWCNTs to increase electrons availability at the CeO2 surface was also evidenced. In the nanocomposite, where the MWCNTs are covered by nanometric-thick CeO2, the oxide layer is thin enough to allow efficient charge transport through it and fast electron transfer at the surface where CO2 is adsorbed. The interconnection of the various components has been shown to be fundamental for the efficient CO2 reduction to formic acid with this new metal-free nanocomposite, and opens new possibilities in the design of optimized electrocatalytic materials. ! Figure 1: a) plot of the Faradaic Efficiency for formic acid production as a function of the overpotential and b) schematic representation of CO2 reduction on MWCNT@CeO2 with highlighted the path to formic acid production favored on partially reduced CeO2-x References [1] A.M. Appel et al. Chem. Rev. 2013, 113, 6621-6658. [2] a) Z. Cheng, B.J. Sherman and C.S. Lo, J. Chem. Phys., 2013, 138, 014702. b) P.M. Albrecht, D. Jiang and D.R. Mullins, J. Phys. Chem. C, 2014, 118, 9042−9050. 137 | P74 SYNTHESIS OF NEW 1-PHENYLPYRROLE BASED MOLECULES FOR DYE-SENSITIZED SOLAR CELLS Tamás Hergert,a Béla Mátravölgyi,b Angelika Thurner,b Alessandro Mordini,c Ferenc Faigla,b a Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1111, Budapest, Hungary. b MTA-BME Organic Chemical Technology Research Group, Hungarian Academy of Sciences, H-1111, Budapest, Hungary. c Department of Organic Chemistry, University of Florence, 50019 - Sesto Fiorentino Italy. e-mail: [email protected] In the last century our energy consumption has grown considerably, mainly based on fossil energy. With the depletion of the sources more and more attention is given for renewable energies. From these the solar cells have the most potential, which convert the radiation of the Sun into electrical energy. Compared to other renewable technologies, the traditional semi-conductor based solar cells are at a disadvantage because of their great cost of manufacture, but despite this they are still an object of great interest being a true renewable energy. A great breakthrough in this field was the so called Grätzel-cell,[1] which used a metal based organic complex to convert energy. The new way of research of the dye sensitized solar cells (DSSC) is the making of an efficient but metal free dye.[2] Solar cells made with such organic compounds have become a considerable field of research because they can be produced at low cost, and has a broad spectrum of usage. During our research work we studied the synthesis of a dye molecule containing 1-phenylpyrrol linker (π-bridge) (3). Our aim was the making of the dihalogenide (2) from jodo- or bromoanthranilic acid (1) and studying the selective coupling of this compound, with finding the most efficient transition metal catalyst and optimizing the conditions of the reaction. We successfully prepared derivatives containing both one and two tiophene rings, their characterization as dyes in solar cells is in progress. References [1] O’Regan, B.; Grätzel, M.: Nature 1991, 353, 737. [2] Mishra, A.; Fischer, M. K. R.; Bäuerle, P.: Angew. Chem. Int. Ed. 2009, 48, 2474. P75 | 138 PHOTOCATALYTIC HYDROGEN PRODUCTION MATERIALS AND DEVICES Gian Luca Chiarello, Maria Vittoria Dozzi, Elena Selli* Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, Milano, Italy. e-mail: [email protected] The photocatalytic production of hydrogen represents a fascinating way to convert and store solar energy in the form of chemical energy, i.e., as hydrogen, the cleanest energy vector for the future. Hydrogen can be produced either by the photocatalytic direct splitting of water into H2 and O2, or, more efficiently, in the presence of sacrificial reagents, in the so-called photoreforming of organics, in either liquid and gas phase. The main challenge is the electronic structure engineering of photocatalytic materials, which should be able to harvest solar radiation producing electron-hole couples and to ensure efficient charge separation to achieve electron transfer reactions, finally leading to solar energy driven thermodynamically up-hill processes. In recent years we systematically investigated both the mechanistic aspects of water photosplitting and of photoreforming of organics [13] and the development of innovative photocatalytic A hν ν materials, based on the engineering of their electronic structure [4], on solid solutions produced by different e H2 h O2 techniques, on the modification of the surface 2H properties by noble metals or co-catalysts to achieve HO increased charge separation [1,5]. Both standard and TiO Ti Pt sophisticated techniques, such as time-resolved nanotube Nafion 117 luminescence [6] and transient absorption measurements [7], were employed to systematically characterize such materials, in relation to their photoactivity. Innovative technologies, including radio frequency magnetron sputtering [8] and flame spray pyrolysis [5], together with electrochemical growth of nanotube arrays [9,10] to obtain photoactive electrodes, were explored with the final aim of producing photocatalytic systems in integrated form to be employed within devices for pure hydrogen production from water solutions [8-10]. - CB + VB + 2 2 References [1] Chiarello, G.L.; Aguirre, M.H.; Selli E. J. Catal. 2010, 273, 182. [2] Chiarello, G.L.; Ferri, D.; Selli, E. J. Catal. 2011, 280, 168. [3] Chiarello, G.L.; Selli, E. in Advances in Hydrogen Production, Storage and Distribution, Woodhead Publishing Series in Energy, 2014, 63, 216. [4] Dozzi, M.V. ; Selli, E. J. Photochem. Photobiol. C 2013, 14, 13. [5] Chiarello, G.L.; Dozzi, M.V.; Scavini, M.; Grunwaldt, J.D.; Selli, E. Appl. Catal. B: Environ. 2014, 160, 144. [6] Dozzi, M.V.; D’Andrea, C.; Ohtani, B.; Valentini, G.; Selli, E. J. Phys. Chem. C 2013, 117, 25586. [7] Grigioni, I.; Stamplecoskie, K.G.; Selli, E.; Kamat, P.V. J. Phys. Chem. C 2015, 119, 20792. [8] Selli, E.; Chiarello, G.L.; Quartarone, E.; Mustarelli, P.; Rossetti, I.; Forni, L. Chem. Commun. 2007, 5022. [9] Altomare, M.; Pozzi, M.; Allieta, M.; Bettini, L.G.; Selli, E. Appl. Catal. B: Environ. 2013, 136, 81; Altomare, M. et al.; Selli, E.; Schmuki P. J. Am. Chem. Soc. 2015, 137, 5646. [10] Chiarello, G.L.; Zuliani, A.; Ceresoli, D.; Martinazzo, R.; Selli, E. ACS Catal. 2016. 139 | P76 BIOFUELS FROM URBAN SEWAGE SLUDGE: A NEW EFFICIENT AND SUSTAINABLE PROCESS TO TURN WASTE INTO A NEW FEEDSTOCK Carlo Pastore, Luigi di Bitonto, Giuseppe Mascolo CNR-IRSA (Istituto di Ricerca Sulle Acque, Viale De Blasio, Bari, Italy e-mail: [email protected] A very detailed study was carried out on separation of lipids from wet sewage scum taken from several wastewater treatment plants (WWTPs). A solvent-less separation of lipids was optimized by simply heating sewage scum at 353 K and centrifuging the heated mass at 4000 rpm per 1 min [1]. Recoverability of 93-99% of total oils was determined. Extracted lipids have a very similar composition in terms of free fatty acids (FFAs), calcium soaps (32-40%wt) and glycerides (mono-, di- and tri-glycerides were practically absents), as well as fatty acid profiles in all of samples studied. Since mainly composed of FFAs, once separated, lipids were converted into biodiesel through a direct esterification process. Reaction conditions were optimised using the desirability function applied on the response surface methodology analysis of a Box–Behnken factorial design of experiments. By carrying out the reaction at 72°C for 120 min and using AlCl3·6H2O as a catalyst (1.5% mol of Al respect to fatty acids), almost 94% of the starting acids were converted into methyl esters [2]. At the end of the reaction, a biphasic system was obtained in which the upper methanolic phase, which contained most of the starting catalyst, was separated from the heaviest phase, mainly composed of fatty acid methyl esters. Such a distribution not only allowed the biodiesel to be easily separated, but also catalysts were efficiently recovered and reused for at least four times, determining a total TON greater than 200,without revealing any loss of its activity [3]. This efficient separation between biofuel produced and unreacted methanol allow a three sequential batch reactors to be run, in which methanol and catalysts were charged in counter current respect to starting feedstock. In this way, the complete conversion (>99%) of starting FFAs into FAMEs was perfectly matched with using the minimum amount of reactants under very mild conditions (345 K, 2 h). The overall convenience of the process was completed by the anaerobic digestion of fibrous residues obtained from centrifugation of starting sewage scum: the final biogas resulted largely enough to sustain the overall heat of process [4]. References [1] di Bitonto, L.; Lopez, A.; Mininni, G.; Mascolo, G.; Pastore, C. Renew. En. 2016, 90, 55. [2] Pastore, C.; Lopez, A.; Mascolo G. Bioresour. Technol. 2014, 155, 91. [3] Pastore, C.; Barca, E.; Del Moro, G.; Lopez, A.; Mininni, G.; Mascolo, G. Appl. Catal. A: General 2015, 501, 48. [4] Pastore, C.; Pagano, M.; Lopez, A.; Mininni, G.; Mascolo, G. Water Science & Technology 2015, 71, 1151. P77 | 140 VALORIZATION OF POLYSTYRENE WASTE FOAM AS POLYMER/CLAY NANOCOMPOSITE: APPLICATION AS METHANOL FUEL CELL MEMBRANE Stouri Mbarek, Bekri Imen, Srasra Ezzedine a a National Research Center for Materials Science, Laboratory of Physical Chemistry of Minerals and Materials Applications ,Technopole Borj Cedria Tunisia e-mail: [email protected] , [email protected] [email protected] Polymer clay nanocomposites can be prepared via several differents methods, including in situ polymerization, melt compounding, or solution intercalation. In this paper, we investigate the solution intercalation method to valorize polystyrene foam waste as nanocomposite. A second step of this work is using this new valorized material as methanol fuel cell membrane. In this context, we have tested thepermeability behaviour toward methanol and the water uptake. The sulfonation of polystyrene has been carried out using H2SO4 as sulfonating agent and (CHCl3) as a solvent to dissolve polystyrene waste and to disperse the clay pallets. We have tested naturel clay without modification and an acid treated one while we have varied the proportion of clay to polymer from 1 to 5 wt%. These nanocomposites were characterized by X-ray diffraction, scan electron microscopy, thermogravimetric analysis(TGA) and calorimetry. The water absorption of the membranes is usually defined in weight percent with respect to the weight of the dry membrane. The membranes initially absorbed large amount of water, which was followed by only a gradual raise in absorption towards the saturation point. The effect of montmorillonite clay on exfoliatione behavior, degree of sulfonation and cristallinity of sulfonated ionomer nanocomposites was systematically studied. X-ray diffraction and SEM were used to evaluate the dispersion of clay platelets within sulfonated ionomer matrices. Experimental results obtained from XRD and SEM revealed a predominately exfoliated morphology within the sulfonated polystyrene ionomer containing 1-5 wt% of clay and acid treated clay. Keywords: chemical modification;In situ Polymerization; polystyrene; sulfonated of polystyrene; Nanocomposites; Physico-chimique and properties applications; Solvent absorption. 141 | P78 NANOCOMPOSITE MEMBRANES BASED ON PBI AND ZrO2 FOR HT-PEMFCS Keti Vezzù,a,* Graeme Nawn,a Enrico Negro,a,b Federico Bertasi,a,b,c Giuseppe Pace,b Antoine Bach Delpeuch,a Gioele Pagot,b Yannick Herve Bang,a Chuanyu Sun,b Vito Di Notod,b,c a Department of Industrial Engineering, University of Padova, Via F. Marzolo 9, I-35131 Padova, Italy. Consorzio Interuniversitario Nazionale per la Scienza e la Tecnologia dei Materiali, INSTM, Italy b CNR-IENI, Via Marzolo 1, I-35131 Padova (PD), Italy. d Department of Industrial Engineering, University of Padova, Via F. Marzolo 9, I-35131 Padova, Italy. b e-mail: [email protected] Fuel cells (FCs) are able to convert the chemical energy stored in hydrogen into electrical energy with a very high efficiency, up to two-three times higher in comparison with traditional internal combustion engines, and do not produce greenhouse gas emissions. Despite these attractive features, FCs do not experience a widespread market penetration yet owing to a variety of drawbacks including expensive functional materials, complex and/or bulky power plants and an insufficient durability. Among the FC families, high-temperature proton exchange membrane fuel cells (HTPEMFCs) show great promise to provide a viable solution to the shortcomings mentioned above. HT-PEMFCs operate at a high temperature, 120 < T < 250°C; in these conditions, the electrocatalysts are not poisoned easily by the most common contaminants found in the reactant streams (e.g., CO in the H2 fuel). Furthermore, HTPEMFCs do not require external humidification. In summary, HT-PEMFCs can be very compact, resulting particularly suitable for application in the automotive sector. The state of the art of electrolyte membranes for application in HT-PEMFCs consists in a polymer characterized by a high thermal and chemical stability such as polybenzimidaziole (PBI), which is doped with H3PO4. In this work, a new family of hybrid inorganic-organic PEM is developed, based on PBI and nanometric ZrO2 with formula PBI/(ZrO2)x with x ranging from 0.7 to 16 wt%. ZrO2 are chosen as the filler for their high chemical stability in an acid environment and for the ZrO2 – PBI interactions in membranes. This feature is expected to give rise to strong interactions between the different components constituting the final hybrid inorganic-organic membranes (i.e., PBI, H3PO4 and ZrO2), thus improving their conductivity, thermal and mechanical properties. The membranes are obtained by solvent-casting processes, and undergo an extensive characterization. ICP-AES and microanalysis are used to determine the chemical composition of the membranes; HR-TG is adopted to study their thermal stability, while the thermal transitions are investigated by DSC. The structure of the proposed membrane is studied by FT-MIR ATR vibrational spectroscopy; the electric behavior is characterized by broadband electrical spectroscopy in the 5 – 190°C and 1 – 106 Hz temperature and frequency ranges, respectively. It is observed that, with respect to pristine PBI, in the hybrid membranes the condensation of H3PO4 to H4P2O7 is brought to higher temperatures. Furthermore, the conductivity at 190°C of the membrane including 10 wt% of ZrO2 is higher in comparison with pristine PBI (4.65·10-2 S/cm and 4.46·10-2 S/cm, respectively). The integration of the results allows to shed light on the complex interplay between the structural features, the thermal properties and the electrical response of this family of hybrid inorganic-organic proton conducting membranes. P79 | 142 A SELF-POWERED SUPERCAPACITIVE MICROBIAL FUEL CELL Carlo Santoro,a Alexey Serov,a Plamen Atanassov, Soavib* a Catia Arbizzani b,* , Francesca a Department of Chemical & Biological Engineering, Center for Micro-Engineered Materials (CMEM), University of New Mexico, Albuquerque, NM 87131, USA. b Department of Chemistry “Giacomo Ciamician”, Alma Mater Studiorum - University of Bologna, Italy. e-mail: [email protected] Microbial fuel cell (MFC) is an emerging biotechnology used for wastewater treatment and simultaneous energy production. Nowadays, the current/power produced from MFC systems is 2-3 orders of magnitude lower compared to traditional PEMFC. Important efforts have being used to increase MFC power output. Here, we demonstrate a novel system with the integration of a microbial fuel cell (MFC) with an internal supercapacitor (SC). The system was able of boosting up the power output of the MFC by exploiting the capacitive features of the MFC carbonaceous electrodes: low potential due to the anaerobic conditions of the bacteria on the carbon brush anode and the high potential operation of ORR electrocatalyst on the cathode. The system suffered of high ohmic losses mainly due to the cathode. In order to further increase the performances, different strategies have been pursued: i) cell voltage has been increased by the use of high potential cathodes like enzymaticbased (bilirubin oxidase, BOx) or iron-based (iron-aminoantipyrine, Fe-AAPyr); ii) overcome the cathode losses with the utilization an additional capacitive electrode (additional electrode, AdE) short-circuited with the MFC cathode and coupled with the MFC anode (MFC-AdE). The utilization of both strategies simultaneously (use of BOx cathode and low impedances of the AdE) allowed to achieve the highest power value ever recorded for MFC that was 84.4 Wm-2 and 152 Wm-3. In this work, the results of galvanostatic (GLV) discharge pulses at different currents (1-45 mA) on MFC-AdE systems featuring different ORR cathodes (AC-, Fe-, and BOx- based) are here reported and discussed. Acknowledments. CS was funded by the Electrochemical Society and Billl & Melinda Gates Foundation under initiative: “Applying Electrochemistry to Complex Global Challenges” FS acknowledges financial support by Università di Bologna (Researcher Mobility Program). Reference [1] Santoro, C.; Soavi, F.; Serov, A.; Arbizzani, C.; Atanassov, P. Biosens. Bioelectron. http://dx.doi.org/10.1016/j.bios.2015.11.026. 143 | P80 DYE-SENSITIZED PHOTOCATALYTIC H2 PRODUCTION: ENHANCED ACTIVITY IN A GLUCOSE DERIVATIVE OF A PHENOTHIAZINE DYE Bianca Cecconi,a Norberto Manfredi,a Riccardo Ruffo,a Valentina Calabrese,b Alberto Minotti,b Francesco Peri,*b Tiziano Montini,c Paolo Fornasiero,*,c Alessandro Abbotto*,a a Department of Materials Science and Solar Energy Research Center MIB-SOLAR, University of Milano-Bicocca, and INSTM Milano-Bicocca Research Unit, Milano, Italy. b Department of Biotechnology and Biosciences, University of Milano-Bicocca, Piazza della Scienza, 2, 20126 Milano, Italy. c Department of Chemical and Pharmaceutical Sciences, University of Trieste, ICCOM-CNR Trieste Research Unit, and INSTM Trieste Research Unit, Trieste, Italy. e-mail: [email protected] Replacement of fossil fuel sources with renewable ones needs to answer to both the demand of electricity and fuels. Nowadays almost all the energy produced with renewable sources is in the form of electricity while research for a future clean fuel is still at the beginning. Hydrogen is considered a promising candidates but unfortunately it is not present on Earth, but it should be obtained from other molecules, such as water, and solar radiation could be used to run the desired splitting reaction. We modified DSSC working mechanism to produce hydrogen thanks to a platinum catalyst. Focusing attention on the role played by the sensitizer, we modified a known dye in the literature, PTZ2, [1] that is a phenothiazine donor core with a di-branched structure.[2] The octyl chain on the phenothiazine nitrogen is not the best option to have proper wettability of TiO2 surface in aqueous solution, thus we replaced it by a glycolic chain and a glucose unit, getting higher surface wettability and enhanced hydrogen production efficiencies for the glucose derivative compared to the glycolic one (Figure 1). A further role of the sugar in self-assembly of dye molecules on semiconductor surface could be envisaged, thanks to the good donor and acceptor character of carbohydrates in hydrogen bonding. The potential role of the sugar in self assembly has been further investigated through the use of carbohydrate spacers as coadsorbents. References [1] Cecconi, B.; Manfredi, N.; Ruffo, R.; Montini, T.; Romero-Ocaña, I.; Fornasiero, P.; Abbotto, A. ChemSusChem 2015, in press, 10.1002/cssc.201501040. [2] Manfredi, N.; Cecconi, B.; Abbotto, A. Eur. J. Org. Chem. 2014, 7069 NEW SYNTHETIC STRATEGIES FOR INCORPORATION OF FLUOROPHORES INTO SAPONITE Valentina Toson,a Claudia Barolo,b Enrico Boccaleri,a Diego Antonioli,aValentina Gianotti,a Marco Milanesioa a UPO, Dipartimento di Scienze ed Innovazione Tecnologica, via Teresa Michel 11, Alessandria, Italy b UniTo, Dipartimento di Chimica and NIS Interdepartmental Centre, Via P.Giuria 7,10125 Torino, Italy e-mail: [email protected] In recent years, the interest in the synthesis of organo-clays materials has increased, because the co-presence of different functionalities in the same material can be exploited for several applications such as catalysis, drug delivery, optoelectronics, and nanocomposites. The aim of the study was synthetizing low cost, stable and efficient light harvester hybrid organo-saponites. The synthetic saponite, a trioctahedral 2:1 clay mineral belonging to the smectite group (Mn+x/n[Mg]6(OH)4[Si8-xAlx]O20·mH2O), was selected like layered inorganic matrix. So far, on the basis of the ionic exchange mechanism, only cationic chromophores can be introduced into negative saponite lamellae, generally by postsynthesis ion exchange. Two different methodologies toprepare of the synthetic organomodified clays hosting a neutral molecule, reducing the reaction time and resources, were developed. Fluorene was chosen as a low cost probe fluorophore, for the cointercalation in saponite with CTA+ cations to compensate the anionic charge of the layer. One-pot synthesized CTA-Fluorene-Saponite was obtained by direct introduction of CTABr surfactant and fluorene in the synthesis gel of saponite, modifying the method proposed by Bisio et al.1 with a H2O/Si molar ratio equal to 110. Liquid assisted grinding method,2 optimized for cationic LDH matrix, was firstly adapted for anionic saponite organic modification. The obtained samples showed different properties, probably because the operative conditions. The unprecedented application of TG-GC-MS in saponite field, allowed detecting the dissolved fluorene into CTA+ chains. The mechanochemical method was selected for the synthesis of fluorophores-saponite, because the sample distribution appeared more homogeneous and the operative conditions were less drastic. Afterward, a new fluorophores (GAM235) was exploited for the first time as light harvester and energy downshifting molecule in photovoltaic field (thanks to its Stokes shift equal to 137nm). The advantages of intercalation into lamellae are the decrease the quenching effect, normally caused by aggregation, and, the host–guest interactions, that can affect the distribution and orientation of guests in the host, leading to the increase of thermal and photochemical stability. The optical features were investigated by DR-UV-Vis spectroscopy and fluorescence. The Stokes Shift of dye was decreased only of 25 nmwith respect to GAM235 in solution. The amount of GAM235 was achieved analyzing the thermal stability by TGA, the elemental analysis by CHN and TG-GCMS results. Hence, LAG method allowed the homogenous dissolution of GAM235, increasing the thermal and photochemical stability and keeping the optical properties. References [1] Bisio, C.; Carniato, F.; Paul, G.; Gatti, G.; Boccaleri, E.; Marchese, L. Lang. 2011, 27, 7250. [2] Conterosito, E.; Van Beek, W.; Palin, L.; Croce, G.; Perioli, L.; Viterbo, D.; Gatti, G.; Milanesio, M. Cryst. Growth Des. 2013, 13, 1162. 145 | P80 ARTIFICIAL PHOTOSYNTHESIS: CAPTURE AND VALORIZATION OF CO2 VIA SURFACE DECORATION OF MWCNT WITH AMINES Cosimo Annese,a Roberto Comparelli,b Pietro Cotugno,a Lucia D’Accolti,*,a,c Antonio Monopoli,a Angelo Nacci,*,a,c Francesca Petronella,b Anna Moliterni,d Aurelia Falcicchio,d and Caterina Fusco*,c a Dipartimento di Chimica, Università di Bari, via E. Orabona 4, 70125 Bari, Italy IPCF-CNR, via E. Orabona 4, 70125 Bari, Italy c ICCOM-CNR, via E. Orabona 4, 70125 Bari, Italy d IC-CNR, via Amendola 122/O, 70126 Bari, Italy e-mail: [email protected] b During the past decade, a great deal of attention has been dedicated to converting solar energy into chemical energy in the form of so-called “solar fuels”, such as H2, methanol, methane, formic acid, etc. In this context, the reduction of carbon dioxide is gaining more and more importance in the research area of chemistry and materials, not only for solving the problems resulting from environmental pollution, but also for finding ways to maintain the carbon resources which are being depleted by the burning of fossil fuels. A very promising method is the photoreduction of CO2 to produce clean fuels under sunlight irradiation, thus mimicking the natural photosynthesis in plants. In this work, nanocomposites composed of titania and amine-grafted multiwalled carbon nanotubes (MWCNT), properly prepared by chemical functionalization via oxirane ring opening with branched polyethylenimine (PEI), behave as both efficient CO2 sorbents and photoreduction catalyst systems in the one-pot sequential process of CO2 capture and reduction, using water as sacrificial reductant. PEI-MWCNTs (4)/TiO2 cat. hν (UV-Vis) CO2 O H C H2O, 25 °C, 8 h O + OH CH3 C OH References [1] Kim, D.; Sakimoto, K. K.; Hong, D.; Yang, P. Angew. Chem. Int. Ed. 2015, 54, 2. [2] Liu, N.; Dasgupta, P.; Yang, P. Chem. Mater. 2013, 25, 415. [3] Ying, L.; Sheng, Z.; Jianmei, L.; Yajun, W.; Guiyuan, J.; Zhen, Z.; Bing, L.; Xueqing, G.; Aijun, D.; Jian, L. Appl. Catal., B 2015, 168-169, 125. [4] Mele, G.; Annese, C.; De Riccardis, A.; Fusco, C.; Palmisano, L.; Vasapollo, G.; D’Accolti, L. Appl. Catal., A 2014, 481, 169. [5] Calo, V.; Nacci, A.; Monopoli, A.; Fanizzi, A. Org. Lett. 2002,4, 2561. LIST OF PARTICIPANTS 147 | List of Partecipants Alessandro Abbotto Università degli Studi di Milano Bicocca via Cozzi 55 20133, Milano, Italy [email protected] Catia Arbizzani Alma Mater Studiorum Università di Bologna via Selmi 2 40126, Bologna, Italy [email protected] Nicola Armaroli Nicolas Alonso-Vante Université de Poitiers 4 rue Michel Brunet F-86022, Poitiers, France ISOF-CNR via Gobetti 101 40129, Bologna, Italy [email protected] [email protected] Roberto Avolio Julia Amici Politecnico di Torino C.so D.ca degli Abruzzi, 24 10129, Torino, Italy IPCB-CNR via Campe Flegrei 34 80078, Pozzuoli, Italy [email protected] [email protected] Vincenzo Baglio Cosimo Annese Università degli Studi di Bari via E. Orabona 4 70125, Bari, Italy CNR-ITAE salita S. Lucia sopra Contesse, 5 98126, Messina, Italy [email protected] [email protected] Laura Baldini Simone Angioni Università degli Studi di Pavia via Taramelli, 12 27100, Pavia, Italy Dip.to di Chimica, Università di Parma parco Area delle Scienze, 17/a 43124, Parma, Italy [email protected] [email protected] Clara Baldoli Baptista Antonio University of Sao Paulo USP Piracicaba,Sao Paulo, Brazil [email protected] CNR-ISTM via C. Golgi 19 20133, Milano, Italy [email protected] List of Partecipants | 148 Nadia Barbero Francesco Barzagli Università degli Studi di Torino ICCOM - CNR via Giuria 7 via Madonna del Piano 10 10125, Torino, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Giuseppe Barbieri Riccardo Basosi CNR-ITM Università degli Studi di Siena via Pietro BUCCI via A. Moro 2 87036, Rende CS, Italy 53100, Siena, Italy [email protected] [email protected] Simona Barison Federico Bella CNR-IENI Politecnico di Torino via Stati Uniti 4 Corso Duca degli Abruzzi 24 35127, Padova, Italy 10129, Torino, Italy [email protected] [email protected] Claudia Barolo Fabio Bellina Universita' degli Studi di Torino Università degli Studi di Pisa via Pietro Giuria 7 via G. Moruzzi, 13 10125, Torino, Italy 56124, Pisa, Italy [email protected] [email protected] Massimo Baroncini Marco Bellini Università degli Studi di Bologna ICCOM-CNR via Selmi 2 via Madonna del PIano 10 40126, Bologna, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Matteo Bartolini Sandra Belviso Università degli Studi di Firenze Università degli Studi della Basilicata via della Lastruccia 3 via Ateneo Lucano 10 50019, Sesto Fiorentino (FI), Italy 85100, Potenza, Italy [email protected] [email protected] 149 | List of Partecipants Elisabetta Benazzi Simona Binetti University degli Studi di Ferrara Università degli Studi di Milano Bicocca Via Fossato di Mortara, 17 via Cozzi 55 44121, Ferrara, Italy 20133, Milano, Italy [email protected] [email protected] Enrico Berretti Chiara Liliana Boldrini Università degli Studi di Firenze Università degli studi di Milano-Bicocca via della Lastruccia 3/13 Via R. Cozzi 55 50019, Sesto Fiorentino (Fi), Italy 20125, Milano, Italy [email protected] [email protected] Federico Bertasi Marcella Bonchio Università degli Studi di Padova Università degli Studi di Padova Via Marzolo 1 via Marzolo, 1 35131, Padova, Italy 35100, Padova, Italy [email protected] [email protected] Federica Bertini Alessandro Boni ICCOM - CNR Universita' degli Studi Di Bologna Via Madonna del Piano 10 via Francesco Selmi 2 50019, Sesto Fiorentino (FI), Italy 40126, Bologna, Italy [email protected] [email protected] Matteo Bessi Silvia Bordiga Università degli Studi di Siena Università degli Studi di Torino Via A. Moro 2 via Filadelfia 51 53100, Siena, Italy 10125, Torino, Italy [email protected] [email protected] Ottavia Bettucci Filippo Bossola Università degli Studi di Siena Università degli Studi dell'Insubria Via A. Moro 2 via Valleggio, 11 53100, Siena, Italy 22100, Como, Italy [email protected] [email protected] List of Partecipants | 150 Riccardo Brandiele Sebastiano Campagna Università degli Studi di Padova Università degli Studi di Messina via Santa Croce 68 viale Ferdinando Stagno d'Alcontres, 31 37032, Monteforte D'Alpone, Italy 98166, Messina, Italy [email protected] [email protected] Maurizio Bruschi Stefano Carli DISAT, Università degli Studi di Milano Universtà degli Studi di Ferrara Bicocca via Fossato di Mortara, 17 piazza della scienza 1 44121, Ferrara, Italy 20126, Milano, Italy [email protected] [email protected] Bianca Cecconi Sergio Brutti Università degli Studi della Basilicata v.le dell'Ateneo Lucano 10 85100, Potenza, Italy [email protected] Martina Cacciarini Università degli Studi di Firenze via della Lastruccia 3 Università degli Studi di Milano Bicocca via Cozzi 55 20133, Milano, Italy [email protected] Luciano Celi DICAM, Università degli Studi di Trento Via Mesiano, 77 50019, Sesto Fiorentino (FI), Italy 38123, Trento, Italy [email protected] [email protected] Massimo Calamante Cosimo Vincenzo Ciasca ICCOM-CNR Università degli studi di Bari Via Madonna del Piano 10 via Orabona 4 50019, Sesto Fiorentino (FI), Italy 70125, Bari, Italy [email protected] [email protected] Laura Calvillo-Lamana Stefano Cimino Università degli Studi di Padova Istituto Ricerche sulla Combustione via Marzolo, 1 P.le V. Tecchio 80 35131, Padova, Italy [email protected] 80125, Napoli, Italy [email protected] 151 | List of Partecipants Nicola Cioffi Lorenzo Cupellini Università degli Studi di Bari Università degli Studi di Pisa via Orabona 4 Via Giuseppe Moruzzi, 13 70125, Bari, Italy 56124, Pisa, Italy [email protected] [email protected] Francesca Colò Vladimiro Dal Santo Politecnico di Torino ISTM-CNR Corso Duca degli Abruzzi, 24 Via Golgi 19 10129, Torino, Italy 20133, Milano, Italy [email protected] [email protected] Matteo Compagnoni Nicola Dalle Carbonare Università degli Studi di Milano Università degli Studi di Ferrara Via Antonio Maffi 13 CNR/ISOF 20162, Milano, Italy via Fossato di Mortara 17-27 [email protected] 44121, Ferrara, Italy [email protected] Andrea Comparini Università degli studi di Firenze via della Lastruccia 3 50019, Sesto Fiorentino (FI), Italy [email protected] Antonio De Luca Università degli Studi di Firenze via della Lastruccia 3 50019, Sesto Fiorentino (FI), Italy Valeria Conte [email protected] Università degli Studi di Roma "Tor Vergata" Alessio Dessì via della Ricerca Scientifica snc CNR-ICCOM 00133, Roma, Italy Via Madonna del Piano 10 [email protected] 50019, Sesto Fiorentino, Italy [email protected] Valeria Criscuolo Università degli Studi di Napoli Gabriele Di Carlo via Cinthia 4 Università degli Studi di Milano 80126, Naples, Italy via Golgi, 19 [email protected] 20133, Milan, Italy [email protected] List of Partecipants | 152 Mariangela Di Donato Monica Fabrizio LENS CNR IENI via N. Carrara 1 via Pastore 24 50019, Sesto Fiorentino (FI), Italy 30031, Dolo, Italy [email protected] [email protected] A. Evelyn Di Mauro Lucia Fagiolari CNR-IPCF-Bari Division Università degli Studi di Perugia Via Orabona 4 via Elce di Sotto, 8 70126, Bari, Italy 6123, Perugia, Italy [email protected] [email protected] Vito Di Noto Gianluca Farinola Università degli Studi di Padova Università degli Studi di Bari Via F. Marzolo 1 via Orabona 4 35131, Padova, Italy 70125, Bari, Italy [email protected] [email protected] Giuliana d'Ippolito Federica Faroldi Istituto di Chimica Biomolecolare CNR Università degli Studi di Parma Via Campi Flegrei 34 Parco Area delle Scienze 17/A 80078, Pozzuoli (Napoli), Italy 43124, Parma, Italy [email protected] [email protected] Christian Durante Maurizio Ferretti Università degli Studi di Padova Università degli Studi di Genova via Marzolo, 1 Via Dodecaneso 31 35100, Padova, Italy 16146, Genova, Italy [email protected] [email protected] James Durrant Maria Gelsomina Folliero Imperial College ICCOM-CNR SW7 2AZ, London, United Kingdom Via Madonna del PIano 10 [email protected] 50019, Sesto Fiorentino (FI), Italy [email protected] 153 | List of Partecipants Paolo Fornasiero Andrea Giaccherini Università degli Studi di Trieste Università degli Studi di Firenze via L. Giorgieri 1 via della Lastruccia 3 34127 Trieste, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Daniele Franchi Walter Giurlani Università degli Studi di Firenze Università Degli Studi di Firenze via della Lastruccia 3 via della Lastruccia 3 50019, Sesto Fiorentino (FI), Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Stefano Freschi Angela Gondolini FRESCHI & VANGELISTI SRL CNR-ISTEC viale Europa, 1 via Granarolo 64 52018, Castel San Niccolò, Italy 48018, Faenza (RA), Italy [email protected] [email protected] Caterina Fusco Luca Gonsalvi Università degli Studi di Bari ICCOM-CNR via E. Orabona 4 Via Madonna del Piano 10 70125, Bari, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Teresa Gatti Gaetano Granozzi Università degli Studi di Padova Università degli Studi di Padova via F. Marzolo 1 via Marzolo, 1 35131, Padova, Italy 35100, Padova, Italy [email protected] [email protected] Claudio Gerbaldi Annalisa Guerri Politecnico di Torino Università degli Studi di Firenze Corso Duca degli Abruzzi 24 via della Lastruccia 3 10129, Torino, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] List of Partecipants | 154 Antonella Guerriero Fabio Invernizzi ICCOM-CNR Università degli Studi di Pavia Via Madonna del PIano 10 Via Taramelli 16 50019, Sesto Fiorentino (FI), Italy 27100, Pavia, Italy [email protected] [email protected] Leonardo Guidoni Sandro Jurinovich Università degli Studi dell'Aquila Università degli Studi di Pisa via Vetoio 2, 67100, Coppito Via Moruzzi 13 67100, L'Aquila, Italy 56124, Pisa, Italy [email protected] [email protected] Anders Hagfeldt Simona la Gatta EPFL Università degli Studi di Bari "Aldo Route Cantonale Moro" 1015, Lausanne, Switzerland via Orabona 4 [email protected] 70124, Bari, Italy [email protected] Tamas Hergert Budapest University of Technology and Economics Andrea La Monaca Università degli Studi di Bologna Műegyetem rkp. 3 via Selmi 2 1111, Budapest, Hungary 40126, Bologna, Italy [email protected] Alessandro Iagatti LENS, INO-CNR via Nello Carrara, 1 50019, Sesto Fiorentino, Italy [email protected] Antonio Laganà Università degli Studi di Perugia via Marzolo, 1 6123, Perugia, Italy [email protected] [email protected] Grazia Leonzio Massimo Innocenti Università degli Studi dell'Aquila Università degli Studi di Firenze Via Giovanni Gronchi 18 – Zona via della Lastruccia 3 industriale di Pile 50019, Sesto Fiorentino (FI), Italy 67100, L'aquila, Italy [email protected] [email protected] 155 | List of Partecipants Federico Locardi Jessica Manzi Università degli Studi di Genova Università degli Studi della Basilicata VIA DODECANESO 31 v.le dell'Ateneo Lucano 10 16136, Genova, Italy 85100, Potenza, Italy [email protected] [email protected] Mariangela Longhi Simone Maranghi Università degli Studi di Milano Università degli Studi di Siena Via Golgi 19 Via Aldo Moro, 2 20133, Milano, Italy 53100, Siena, Italy [email protected] [email protected] Michele Maggini Mauro Marchetti Università degli Studi di Padova ICB-CNR via Marzolo, 1 Traversa La Crucca 3 R. Baldinca LiPunti 35100, Padova, Italy 07100, Sassari, Italy [email protected] [email protected] Mirko Magni Stefano Marchionna Università degli Studi di Milano RSE Spa, Ricerca sul sistema energetico via Golgi 19 Via Rubattino 54 20133, Milano, Italy 20134, Milano, Italy [email protected] [email protected] Francesco Malara Giulia Marianetti ISTM-CNR Scuola Normale Superiore di Pisa via Golgi 19 Piazza dei Cavalieri n°7 20133, Milano, Italy 56017, Pisa, Italy [email protected] [email protected] Norberto Manfredi Alessio Masala Università degli Studi di Milano-Bicocca Università degli Studi di Torino v. R. Cozzi 55 via G. Quarello 15/a 20125, Milano, Italy 10135, Torino, Italy [email protected] [email protected] List of Partecipants | 156 Béla Matravolgyi Hamish Miller Budapest University of Technology and Economics CNR-ICCOM Műegyetem rkp. 3 50019, Sesto Fiorentino, Italy 1111, Budapest, Hungary [email protected] Via Maddona del Piano 10 [email protected] Sara Morandi Stouri Mbarek Università degli studi di Milano ENSCM Chimie Montpellier Via Golgi 19 11 rue Faubour Figurolles 20133, Milano, Italy 34070, Montpellier, France [email protected] [email protected] Alessandro Mordini Irene Mellone ICCOM-CNR ICCOM-CNR Via Madonna del Piano 10 via Madonna del Piano 10 50019, Sesto Fiorentino (FI), Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Adele Mucci Pietro Mendonca de Santis Sica Università degli S. di Modena e R.Emilia College of agriculture "Luiz de Queiroz" via G. Campi 103 Almirante Barroso Street, 338 41125, Modena, Italy 13416398, Piracicaba, Brazil [email protected] [email protected] Ana Belén Muñoz-García Enzo Menna Università degli Studi di Napoli Università degli Studi di Padova Federico II Via Marzolo, 1 Comp. Univ. Monte S. Angelo – Via Cintia 26 35131, Padova, Italy [email protected] 80126, Napoli, Italy [email protected] Raluca Mereu Università degli Studi di Milano Bicocca Dept of Material Science and MIBSOLAR center , Via Cozzi 55 20133, Milano, Italy [email protected] Marco Musiani IENI-CNR Corso Stati Uniti 4 35127, Padova, Italy [email protected] 157 | List of Partecipants Piercarlo Mustarelli Maria Cristina Paganini Università degli Studi di Padova Università degli Studi di Torino via Marzolo, 1 via Giuria 7 35100, Padova, Italy 10125, Torino, Italy [email protected] [email protected] Jijeesh Ravi Nair Maria Pagliaro Politecnico Di Torino ICCOM-CNR Corso Duca degli Abruzzi 24 Via Madonna del PIano 10 10129, TORINO, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] alberto Naldoni CNR – ISTM Via C. Golgi 19 20133, Milan, Italy [email protected] Gioele Pagot Università degli Studi di Padova via Gradenigo 6/a 35131, Padova, Italy [email protected] Maria Assunta Navarra Sapienza University of Rome Monica Panigati Piazzale Aldo Moro 5 Università degli Studi di Milano 185, Rome, Italy Via Golgi, 19 [email protected] 20133, Milano, Italy [email protected] Carlo Nervi Università degli Studi di Torino Fabiola Pantò VIA P. GIURIA 7 Universita' Mediterranea di R. Calabria 10125, Torino, Italy via Graziella, loc. Feo di Vito [email protected] 89122, Reggio Calabria, Italy [email protected] Isabella Nicotera Università degli Studi della Calabria Dept. of Chemistry and Chemical Tecnologies 87036, Rende (CS), Italy [email protected] Francesco Paolucci Università degli Studi di Bologna via Selmi 2 40126, Bologna, Italy [email protected] List of Partecipants | 158 Maria Laura Parisi Maurizio Peruzzini Università degli Studi di Siena ICCOM-CNR Via A. Moro 2 Via Madonna del Piano 10 53100, Siena, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Maurizio Passaponti Rosaria Anna Picca Università degli Studi di Firenze Università degli Studi di Bari via della Lastruccia 3 Via. E. Orabona 4 50019, Sesto Fiorentino (FI), Italy 70126, Bari, Italy [email protected] [email protected] Carlo Pastore Emanuele Piciollo CNR-IRSA (Istituto di Ricerca Sulle Lem srl Socio Unico Acque) via l. Valiani 55/59 Viale De Blasio 5 52021, Levane - Bucine (AR), Italy 70132, Bari, Italy [email protected] [email protected] Maddalena Pizzotti Michele Pavone Università degli Studi di Milano Università degli Studi di Napoli via Golgi 19 Federico II 20133, Milano, Italy COMP. UNIV. MSA VIA CINTIA 21 [email protected] 80126, Napoli, Italy [email protected] Andrea Pucci Università degli Studi di Pisa Nerino Penazzi Via Moruzzi 13 Politecnico di Torino 56124, Pisa, Italy C.so D.ca degli Abruzzi 24 [email protected] 10128, Torino, Italy [email protected] Elsa Quartapelle Procopio Università degli Studi di Milano via Golgi 19 20133, Milano, Italy [email protected] 159 | List of Partecipants Elena Rebollo Francesca Russo CNR-IENI Università degli Studi di Firenze Corso Stati Uniti 4 via della Lastruccia 3 35127, Padova, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] Federica Sabuzi Gianna Reginato Università degli Studi di Roma Tor ICCOM-CNR Vergata Via Madonna del Piano 10 via della Ricerca Scientifica 50019, Sesto Fiorentino (FI), Italy 133, Rome, Italy [email protected] [email protected] Ilenia Rossetti Nicola Sangiorgi Università degli Studi di Milano CNR-ISTEC via C. Golgi 19 via Granarolo 64 20133, Milano, Italy 48018, Faenza (RA), Italy [email protected] [email protected] Ruggero Rossi Alessandra Sanson Università degli Studi di Bologna CNR-ISTEC viale Risorgimento 4 via Granarolo 64 40133, Bologna, Italy 48018, Faenza (RA), Italy [email protected] [email protected] Riccardo Ruffo Saveria Santangelo Università degli Studi di Milano Bicocca DICEAM, Università Mediterranea via Cozzi 55 89122, Reggio Calabria, Italy 20133, Milano, Italy [email protected] [email protected] Caterina Sarno Irene Ruggeri Università degli Studi di Bologna Via Selmi 2 40126, Bologna, Italy [email protected] Università degli Studi di Roma Tor Vergata Via della Ricerca Scientifica 1 133, Roma, Italy [email protected] List of Partecipants | 160 Elena Selli Maria Luisa Testa Università degli Studi di Milano CNR - ISMN via Golgi 19 Via U. La Malfa 153 20133, Milano, Italy 90146, Palermo, Italy [email protected] [email protected] Adalgisa Sinicropi Giuseppe Torzillo Università degli Studi di Siena CNR – ISE Via A. Moro 2 via Madonna del piano, 10 53100, Siena, Italy 50019, Sesto Fiorentino, Italy [email protected] [email protected] Stefania Siracusano Valentina Toson CNR-ITAE Università del Piemonte Orientale Via Salita Santa Lucia sopra Contesse, 5 VIA TERESA MICHELL 11 98126, Messina, Italy 15121, Alessandria, Italy [email protected] [email protected] Maurizio Taddei Giulia Tuci Università degli Studi di Siena ICCOM-CNR Via A. Moro 2 Via Madonna del Piano 10 53100, Siena, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Francesco Tassinari Giovanni Valenti Università degli S. di Modena e R. Emilia Università degli Studi di Bologna Via G. Campi 103 41100, Modena, Italy Via Selmi 2 40126, Bologna, Italy [email protected] [email protected] Federico Valerio Cristina Tealdi Università degli Studi di Pavia Ordine Chimici Liguria VIA MAZZINI 48/1, Viale Taramelli 12 Bogliasco (GE), Italy 27100, Pavia, Italy [email protected] [email protected] 161 | List of Partecipants Svetoslava Vankova Margret Wohlfahrt-Mehrens DISAT, Politecnico di Torino ZSW – und Wasserstoff-Forschung corso Duca degli Abruzzi 24 Helmholtzstrasse 8 10129, Torino, Italy D-89081, Ulm, Germany [email protected] [email protected] Anna Maria Venezia Isabella Zama ISMN-CNR DAUNIA SOLAR CELL via Duca degli Abruzzi 2 via Zuccherificio 10 Palermo, Italy 48123, Mezzano, Italy [email protected] [email protected] Lorenzo Veronese Lorenzo Zani Università degli Studi di Milano ICCOM-CNR via Golgi 19 Via Madonna del Piano 10 20133, Milano, Italy 50019, Sesto Fiorentino (FI), Italy [email protected] [email protected] Daniele Versaci Politecnico di Torino Corso Duca degli Abruzzi 24 10129, Torino, Italy [email protected] Alberto Visibile Università degli Studi di Milano Via Golgi 19 20133, Milano, Italy [email protected] Francesco Vizza ICCOM-CNR Via Madonna del Piano 10 50019, Sesto Fiorentino (FI), Italy [email protected] List of Authors | 162 Abate A. OP25 P36 P02 Abbotto A. OP13 Aricò A.S. P13 Acciarri M. OP54 P63 P80 Armaroli N. KN5 P47 Armiento L. OP35 OP53 Atanassov P. P79 Agnoli S. OP5 Avolio R. P02 Agostiano A. KN4 Baglio V. OP54 OP47 Baglio V. P63 OP49 Baldini L. OP22 Aguiar C.L. Aguilera L. Alberti S. Alidoost M. P49 P25 P50 Baldoli C. P03 P51 Ballarin B. P64 OP10 Bandara T. P71 Bang Y.H. P78 Baptista A.S. P49 P26 OP14 Allieta M. P54 P50 Alonso-Vante N. KN6 P51 Amici J. OP14 Barbero N. P04 P67 Barbieri G. OP21 P01 Baricco M. P48 P17 Barison S. OP9 Annese C. P82 Barolo C. OP37 Antonioli D. P81 P04 Antonucci P. OP6 P81 Angioni S. P60 Baroncini M. OP20 Appetecchi G.B. P53 Barone V. OP39 Aprano S. P22 Barzagli F. P05 Arbizzani C. OP2 P39 Argazzi R. P06 Basosi R. OP31 P58 P46 P79 P62 P23 Battisti L. P32 163 | List of Authors Becerril V.S. P27 Becerril V.S. P71 Bella F. Bellina F. AL Binetti S. P12 OP37 P47 P07 OP53 P19 Biroli A.O. OP45 P29 Bodoardo S. OP14 P30 P67 P53 P68 OP25 P70 OP39 Boccaleri L. P81 Bellini M. P08 Boldrini C.L. P13 Beltram A. OP1 Boldrini S. OP9 Belviso S. OP43 Bolzoni A. P03 Benazzi E. P36 Bonaccorso F. P28 Beneventi D. P30 Berretti E. P09 Bonchio M. P10 Bonchio . KN1 Boni A. P73 Bertasi F. OP46 OP43 OP17 P11 OP17 P56 P57 P78 OP23 Bordiga S. P48 Borsacchi S. OP29 Bessi M. P72 Borzatta V. OP35 Bettucci O. P71 Boshta M. OP53 Biagiotti G. P24 Bossi A. P03 Bianco S. P07 Bossola F. P14 Bignozzi C.A. Bigoni F. OP25 Boutsika L.G. OP44 OP33 Brandiele R. OP45 Breglia R. OP11 P23 Brown T.M. OP43 P36 Brunetti A. OP21 OP2 Bruni G. P15 P01 List of Authors | 164 P65 Bruschi M.B. Brutti S. OP11 OP4 P16 P45 Bussotti L. P24 Cacciarini M. OP24 Calabrese V. P80 Calamante M. OP31 P27 Caratto V. Caravella A. OP21 Carboni M. OP4 Cargnello M. P31 Carli S. OP25 P36 Carraro F. OP5 Carvalho E.M. P49 P50 Carvalho R.S. P71 P72 Calegari R.P. Calvillo L. OP5 Campagna S. KN3 Cannavaro I. P30 Capasso A. Capolupo F. OP43 P09 Casaluci S. Caporali S. P10 Capozzi M.A. P18 Caprasecca S. OP18 P24 Capriati V. P13 Capriccioli A. OP26 Caramori S. OP25 OP33 OP45 P23 P36 P28 OP43 Casarin L. P36 Cattaneo A.S. P17 Cattelan M. OP5 Cavallini M. P21 Cavina M. OP38 Cecconi B. OP13 P21 P31 P49 P50 P49 P50 OP17 Carlà F. P35 P62 P26 P80 Celi L. P32 Cernuschi F. P47 Charalambopoulou G. OP44 Chaussy D. P30 Chiarello G. P75 Ciasca C.V. P18 Cicchi S. P24 Cigarini L. P33 Cimino S. OP34 OP3 OP51 165 | List of Authors Cioffi N. OP51 P09 P31 Dal Santo V. OP1 Cipolla M.P. OP33 P14 Colantoni I. OP16 P52 Coletti G. P12 P54 Colò F. AL P60 P19 P44 Colombo A. OP33 Das K.C. P51 Compagnoni M. OP32 De Gioia L.D. OP11 P20 De Giorgio F. OP2 Comparelli R. P82 Comparini A. P09 Dekel D.R. OP40 P21 Delgado Jaen J.J. OP1 Conte V. P59 Della Volpe C. P32 Correa Baena J.P. OP25 Delpeuch A.B. OP46 Costa G.A. P26 P11 Costantino F. OP15 P78 Cotugno P. P82 Del Rio A.E. OP43 Credi A. OP20 De Luca A. OP16 Criscuolo V. P22 Cugini A. OP41 Dessì A. OP31 Cupellini L. OP18 Destri S. OP49 P24 Destro M. P19 Curcio M. P16 Di Nicola F.P. P64 Curri M.L. OP49 Di Bartolomeo E. P61 D’Acapito F. OP40 Di Benedetto F. OP16 P39 P34 OP16 OP40 P34 OP51 D’Accolti L. P82 P21 d’Ippolito G. OP30 P31 d’Ischia M. P22 P34 Dalle Carbonare N. P23 P09 List of Authors | 166 Di Bitonto L. P76 Fabbri F. P44 Di Carlo A. P28 Fabiani D. P39 OP43 Fabrizio M. OP9 Di Carlo G. OP45 Fagiolari L. OP15 Di Donato M. OP22 Faigl F. P74 P24 Falcicchio A. P82 P35 Fantini S. P53 P72 Fan Y. OP6 Farinola G.M. KN4 Di Mauro A.E. OP49 Di Michele A. P20 OP47 OP46 P18 Di Noto V. P11 Faroldi F. P56 Dipaquale L. OP22 P25 P78 Fasoli M. P26 OP30 Fedeli S. P24 Doglione R. P68 Fedriguccia A. Doria S. P35 Felici R. P31 Dozzi M.V. P75 Ferrara C. P17 Dragonetti C. OP33 Drioli E. OP21 Dulio S. Durante C. OP38 P65 Ferretti M. P26 P37 Filippi J. P08 P15 Fino V. P18 OP50 Fiore A. P18 Durrant J.R. PL01 Fiorilli S. P19 Elamin K. OP10 Floris B. P59 Elm J. OP24 Focarete M.L. P39 Enotiadis A. OP44 Foggi P. P24 Errico M.E. P02 P35 Escolástico S. OP9 P72 Escorihuela S. OP9 Folegatti V. P12 Ezzedine S. P77 Folliero M.G. P08 Fontana A. OP30 167 | List of Authors Fontanesi C. P33 Fornasiero P. P73 Franchi D. Francia C. Giaccherini A. P21 OP1 OP16 OP13 OP51 OP17 P10 P80 P31 P27 P33 P35 P34 OP14 Giambastiani G. OP48 P70 Giamello E. P55 OP28 Giannotti V. P81 OP6 Giannuzzi R. OP33 P60 Gionco C. P55 P27 Giorno L. OP21 P71 Giurlani W. P34 Fusco C. P82 Gobetto R. OP28 Głowacki E.D. KN4 Gonsalvi L. OP23 Gorni G. OP35 Franco F. Frontera P. Furlani M. Galliano S. Galloni P. Gatti T. OP37 P04 Grądzka E. P15 P59 Gräetzel M. OP25 OP27 Granozzi G. OP5 P28 P15 Gatto E. P59 OP50 Gatto I. OP54 Gennaro A. Geppi M. Gerbaldi C. P15 Grätzel M. Greco C. OP50 Griffini G. OP29 Guerriero A. AL OP37 Guidoni L. Hagfeldt A. AL OP11 AL OP23 OP7 AL P07 OP25 P19 P69 P29 PL02 P30 P53 Hergert T. P74 List of Authors | 168 Iagatti A. Imen B. Innocenti M. P24 Le Donne A. P12 P35 P47 P72 OP53 P77 Leftheriotis G. OP16 Lelja F. OP48 Leonzio G. AL OP43 P40 OP51 P41 P09 P42 P10 P43 P21 Libertini E. P64 P31 Licandro E. P03 P33 Licoccia S. P61 P34 Lin R. P53 Invernizzi F. P37 Lisi L. OP34 Jagdale P.V. P30 Locardi F. P26 Locatelli C. P52 Jevric M. OP24 Jurinovich S. P38 Lombardo L. OP10 La Parola V. P66 Longhi M. OP42 OP26 Longoni G. OP8 Laganà A. LaGanga G. KN3 Luconi L. la Gatta S. OP47 Luisetto I. OP48 P61 Lamberti A. P07 Macchioni A. Lamberti A. P19 Maddalena P. P22 La Monaca A. P39 Maglione M.G. P22 Lanfredi L. P37 Magnano G. OP45 Lanzi M. P64 Magni M. OP33 Lasso J. P20 Malara F. OP1 Lavacchi A. OP15 OP40 P52 P08 P54 P09 P60 P21 P44 P31 P34 Manca M. OP33 169 | List of Authors OP34 Masala A. P48 OP3 Mascolo G. P76 OP13 Mastria R. OP49 P13 Matic A. OP10 P80 Mátravölgyi B. P74 P05 Mbarek S. P77 P06 Mecerreye D. P29 Manini P. P22 Meligrana G. P19 Manzi J. P16 Meligrana G. P30 P45 Mellander B. P27 Mancino G. Manfredi N. Mani F. Maranghi S. Marcaccio M. P46 OP17 P71 Mellone I. P24 Melzi R. Marchionna S. P47 Menna E. Marchionni A. P08 Marelli M. OP1 OP27 P28 Mennucci B. OP18 P24 P54 P38 Mercandelli P. P44 Marianetti G. P17 OP40 P60 Maresca G. OP23 P53 P57 P69 Mereu A. OP53 OP25 Merlini M. P47 OP39 Merlo L. P63 María Serra J.M. OP9 Mikkelsen K.V. Mari C.M. OP8 Milanesio M. Marrani A.G. OP4 Milano F. Martelli C. OP35 Martini F. OP29 Martini M. P26 Martinuzzi S. P10 Marzoratia S. OP42 OP24 P81 OP47 KN4 Miller H.A. OP40 P08 Millia L. P01 Minarini C. P22 Minei P. OP29 OP39 List of Authors | 170 Minella M. P70 Mussini P.R. P03 Minero C. P70 Mustarelli P. P01 Minguzzi A. OP19 OP52 P52 P17 Minotti A. P80 P37 Moehl T. P69 P65 Moliterni A. P82 Nacci A. P82 Monini M. P35 Nair J.R. P53 Monopoli A. Montegrossi G. Montini T. P72 AL P82 P19 OP16 P29 P31 P30 P34 Najafib L. OP43 P73 Naldoni A. OP1 OP1 P52 OP13 P54 P80 P60 Morandi S. P52 P44 Mordini A. OP31 Nastasi F. KN3 P27 Navarra M.A. OP10 P62 Nawn G. OP46 P71 P11 P72 P56 P74 P78 Moreno M. P53 Mortalò C. OP9 P11 Morvillo P. OP41 P56 Moukheiber E. P63 P78 Mróz M.M. OP1 Mucci A. OP41 P64 Muñoz-García A.B. Musiani M. OP12 OP3 Negro E. Nelli I. OP46 P26 Nencini L. OP28 Nervi C. OP28 171 | List of Authors Neto J.P. P49 Parenti F. P50 P51 P64 Parisi M.L. Nicotera I. OP44 Nielsen M.B. OP24 Paska Y. Nobili F. OP42 Passaponti M. Nonomura K. Oberhauser W. Omar O.H. Operamolla A. OP47 Outeiro M. Pace G. Paganini M.C. Page M. Pagliaro M.V. Pagot G. Panero S. Panigati M. Pantò F. Paolucci F. Pardi L. OP40 P09 P21 Pastore C. P76 Patané S. P54 KN4 OP47 P46 P62 AL P08 OP41 P60 Patrini M. P37 P49 Pavone M. OP12 P50 Penazzi N. OP14 OP46 P67 P11 P68 P56 P70 P78 Perazzolo V. P55 Peri F. P80 Perna F.M. P13 OP40 P08 Peruzzini M. OP50 OP23 OP46 OP31 P11 P05 P56 P06 P78 P71 OP10 Pescarmona P.P. P19 P57 Petronella F. P82 P69 Pezzella A. P22 OP6 Picca R.A. OP51 P60 P31 OP17 P09 P57 Picelli L. P73 Piciollo E. P32 Pignataro B. Pinna N. OP50 P21 OP27 OP6 List of Authors | 172 Pirri C.F. Ricci M. P65 OP45 Rigato R. P11 Polizzi S. P56 Rizzi G.A. P15 Porcarelli L. P29 Porcarelli L. P53 Pizzotti M. Prato M. P07 OP17 P73 OP50 Rizzo A. OP49 Roberto D. OP33 Romanelli M. OP16 Pretia A. OP38 Romero-Ocaña I. OP1 Psaro R. P54 Romero-Ocaña I. OP13 P44 Rondinini S. OP19 OP29 Rondinini S. P52 OP39 Rossetti I. OP32 Puntoriero F. KN3 Rossetti I. P20 Punzi A. P18 Rossia R. OP38 Quagliotto P. P04 Rossi C.O. OP44 QuartapelleProcopio E. P57 Rossin A. OP48 P69 Ruffo R. OP13 Pucci A. Quartarone E. P17 OP8 P65 P80 P01 Ruggeri G. OP29 Ruggeri I. OP2 Ragazzon G. OP20 Ragnia R. OP47 Rapino S. OP17 Sabuzi F. P59 Rebollo E. OP9 Saccà A. OP54 Recchia S. P14 Saccone D. Reginato G. OP31 P58 Salice P. OP27 P27 Salsamendi M. P29 P35 Sanguineti E. P26 P62 Sansone F. P71 P72 Renzi M. P04 OP22 P25 Santangelo S. OP42 OP6 P54 P60 Ricciardi R. OP41 Santoro C. P79 173 | List of Authors Santoro E. OP43 Steriotis T.A. OP44 OP49 Sariciftci N.S. KN4 Striccoli M. Sarno C. P61 Sun C. P78 Savi F. OP10 Sun J. P14 Schenetti L. OP41 Syrrokostas G. Sebastián D. OP54 Taddei M. AL OP31 Selli E. P75 Serov A. P79 Tagliaferro A. P30 Sesenna A. P25 Tangorra R.R. KN4 Setti L. OP38 P62 Tassinari F. OP41 Shaplov A.S. P29 P64 Siboni S. P32 Tassini P. P22 Sica P. P49 Tealdi C. OP52 P50 P65 P51 Terenziani F. OP22 P49 Tessore F. OP45 P50 Testa M.L. P66 Silvi S. OP20 Thurner A. P74 Simari C. OP44 Tommasi R. Sinicropi A. OP31 Tonello S. P11 P35 Tonoli F.C. P49 Silverio M. P46 Siracusano S. OP49 P50 P62 Torzillo G. OP36 P72 Tosi I. OP22 P63 P25 Sissa C. OP22 Soavi F. OP2 Touloupakis E. P58 Tresso E. P07 P79 Trevizan A. P49 Sottile M. OP29 Trevizan A. P50 Sportelli M.C. OP51 Triolo C. P54 P31 Stassi A. Stelitano S. OP54 OP6 Toson V. P81 OP36 P60 List of Authors | 174 Trotta M. OP47 Vizza F. KN4 Tuci G. OP48 Turri S. AL Tuti S. OP40 P08 Vlachopoulos N. AL Vurro D. P18 P61 Vygodskii Y.S. P29 Ussano E. P24 Wang Y. P14 Valenti G. OP17 Wohlfahrt-Mehrens M. KN2 P57 Zaccaria M. P39 P73 Zafferoni C. OP48 Vankova S. P67 P34 P68 Zakeeruddin S.M. Vanossi D. P33 Zama I. Vázquez-Gómez L. OP3 Zanarini S. Venanzi M. P59 Zani L. Venezia A.M. P66 P27 Venturi M. OP20 P35 Verlato E. OP3 P62 Veronese L. P69 P71 Versaci D. P70 P72 Vertova A. OP19 P52 Vezzù K. OP46 Villa D.C. P17 Virgili T. OP1 Viscardi G. OP37 P04 Visibile A. OP19 Vitillo J.G. P48 Vivani R. OP14 Zheng J. Zolin L. P03 OP15 OP31 Zeng J. P78 Viglianti L. P67 OP49 Zignani S.C. OP35 OP35 Zappia S. P11 Vierucci S. AL P15 OP54 P30 175 | NOTES NOTES | 176 177 | NOTES NOTES | 178 179 | NOTES