BOOK OF ABSTRACT - ENERCHEM-1

Transcript

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
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"
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"
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"
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"
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"
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"
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"
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"
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"
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,
ABSTRACTS
Plenary Lectures (PL01-PL02)
Keynote Lectures (KN01-KN06)
Award Lecture (AL)
Oral Presentations (OP01-OP54)
Posters (P01-P80)
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
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 .
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
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
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
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.
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)
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
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
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
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
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
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
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
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, Aurélie Guéguen, Rémi
Dedryvère, 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)
[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.
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.
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.
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)
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
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)
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.
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
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
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.
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.
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
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
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.
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
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
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
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.
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
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
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.
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.
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
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
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
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.
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.
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
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
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
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
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
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
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
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.
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
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
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
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
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
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.
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.
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.
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
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
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
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.
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.
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.
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
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
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
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
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.
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
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
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
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
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
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.
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.
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.
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
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
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.
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
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
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.
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
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.
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
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
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
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
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
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)
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
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
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
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
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
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
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
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
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
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
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
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
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
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.
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
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
University of Georgia, 597 Brooks Drive, Athens-Ga, USA
3
2
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
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
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
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
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
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
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
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
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
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
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
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,
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
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.
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
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
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
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
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
d
Department of Applied Physics, Chalmers University of Technology, Kemivagen 9, 412 96 Göteborg,
Sweden.
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
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.
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
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.
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.
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
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
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
b
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.
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
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.
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
Abbotto, A. ChemSusChem 2015, in press, 10.1002/cssc.201501040.
[2] Manfredi, N.; Cecconi, B.; Abbotto, A. Eur. J. Org. Chem. 2014, 7069
LIST OF PARTICIPANTS
145 | List of Partecipants
Alessandro Abbotto
Università degli Studi di Milano Bicocca
via Cozzi 55
20133, Milano, Italy
[email protected]
Nicolas Alonso-Vante
Université de Poitiers
4 rue Michel Brunet
F-86022, Poitiers, France
[email protected]
Julia Amici
Politecnico di Torino
C.so D.ca degli Abruzzi, 24
10129, Torino, Italy
[email protected]
Simone Angioni
Università degli Studi di Pavia
via Taramelli, 12
27100, Pavia, Italy
[email protected]
Baptista Antonio
University of Sao Paulo USP
Piracicaba,Sao Paulo, Brazil
[email protected]
Nicola Armaroli
ISOF-CNR
via Gobetti 101
40129, Bologna, Italy
[email protected]
Roberto Avolio
IPCB-CNR
via Campe Flegrei 34
80078, Pozzuoli, Italy
[email protected]
Vincenzo Baglio
CNR-ITAE
salita S. Lucia sopra Contesse, 5
98126, Messina, Italy
[email protected]
Laura Baldini
Dip.to di Chimica, Università di Parma
parco Area delle Scienze, 17/a
43124, Parma, Italy
[email protected]
Clara Baldoli
CNR-ISTM
via C. Golgi 19
[email protected]
Catia Arbizzani
Alma Mater Studiorum Università di
Bologna
Nadia Barbero
Università degli Studi di Torino
via Selmi 2
via Giuria 7
[email protected]
[email protected]
List of Partecipants | 146
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
via Stati Uniti 4
Corso Duca degli Abruzzi 24
35127, Padova, 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
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
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
85100, Potenza, Italy
[email protected]
[email protected]
Francesco Barzagli
Elisabetta Benazzi
ICCOM - CNR
University degli Studi di Ferrara
via Madonna del Piano 10
Via Fossato di Mortara, 17
44121, Ferrara, Italy
[email protected]
[email protected]
Enrico Berretti
Chiara Liliana Boldrini
Università degli studi di Milano-Bicocca
via della Lastruccia 3/13
Via R. Cozzi 55
50019, Sesto Fiorentino (Fi), Italy
[email protected]
[email protected]
Federico Bertasi
Marcella Bonchio
Università degli Studi di Padova
Via Marzolo 1
via Marzolo, 1
[email protected]
[email protected]
Federica Bertini
Alessandro Boni
ICCOM - CNR
Universita' degli Studi Di Bologna
Via Madonna del Piano 10
via Francesco Selmi 2
[email protected]
[email protected]
Matteo Bessi
Silvia Bordiga
Via A. Moro 2
via Filadelfia 51
53100, Siena, Italy
[email protected]
[email protected]
Ottavia Bettucci
Filippo Bossola
Università degli Studi dell'Insubria
Via A. Moro 2
via Valleggio, 11
53100, Siena, Italy
22100, Como, Italy
[email protected]
[email protected]
Simona Binetti
Riccardo Brandiele
via Cozzi 55
via Santa Croce 68
37032, Monteforte D'Alpone, 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
[email protected]
[email protected]
Bianca Cecconi
Sergio Brutti
v.le dell'Ateneo Lucano 10
[email protected]
Martina Cacciarini
via Cozzi 55
[email protected]
Luciano Celi
DICAM, Università degli Studi di Trento
Via Mesiano, 77
38123, Trento, Italy
[email protected]
[email protected]
Massimo Calamante
Cosimo Vincenzo Ciasca
ICCOM-CNR
Università degli studi di Bari
via Orabona 4
70125, Bari, Italy
[email protected]
[email protected]
Laura Calvillo-Lamana
Stefano Cimino
via Marzolo, 1
[email protected]
Istituto Ricerche sulla Combustione
P.le V. Tecchio 80
80125, Napoli, Italy
[email protected]
Sebastiano Campagna
Università degli Studi di Messina
viale Ferdinando Stagno d'Alcontres, 31
[email protected]
Nicola Cioffi
Università degli Studi di Bari
via Orabona 4
70125, Bari, Italy
[email protected]
Francesca Colò
Vladimiro Dal Santo
ISTM-CNR
Corso Duca degli Abruzzi, 24
Via Golgi 19
[email protected]
[email protected]
Matteo Compagnoni
Università degli Studi di Milano
Via Antonio Maffi 13
[email protected]
Andrea Comparini
Nicola Dalle Carbonare
Università degli Studi di Ferrara
CNR/ISOF
via Fossato di Mortara 17-27
[email protected]
Università degli studi di Firenze
Antonio De Luca
[email protected]
Valeria Conte
[email protected]
Università degli Studi di Roma "Tor
Vergata"
Alessio Dessì
via della Ricerca Scientifica snc
CNR-ICCOM
00133, Roma, Italy
[email protected]
50019, Sesto Fiorentino, Italy
[email protected]
Valeria Criscuolo
Università degli Studi di Napoli
via Cinthia 4
80126, Naples, Italy
[email protected]
Gabriele Di Carlo
via Golgi, 19
20133, Milan, Italy
[email protected]
Lorenzo Cupellini
Via Giuseppe Moruzzi, 13
Mariangela Di Donato
LENS
56124, Pisa, Italy
via N. Carrara 1
[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
Via F. Marzolo 1
via Orabona 4
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 Genova
via Marzolo, 1
Via Dodecaneso 31
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]
[email protected]
Monica Fabrizio
CNR IENI
Paolo Fornasiero
via Pastore 24
Università degli Studi di Trieste
30031, Dolo, Italy
via L. Giorgieri 1
[email protected]
34127 Trieste, Italy
[email protected]
Daniele Franchi
Walter Giurlani
Università Degli Studi di Firenze
[email protected]
[email protected]
Carlotta Francia
Angela Gondolini
CNR-ISTEC
C.so D.ca degli Abruzzi 24
via Granarolo 64
48018, Faenza (RA), Italy
[email protected]
[email protected]
Stefano Freschi
Luca Gonsalvi
FRESCHI & VANGELISTI SRL
ICCOM-CNR
viale Europa, 1
52018, Castel San Niccolò, Italy
[email protected]
[email protected]
Teresa Gatti
Gaetano Granozzi
via F. Marzolo 1
via Marzolo, 1
[email protected]
[email protected]
Claudio Gerbaldi
Annalisa Guerri
[email protected]
[email protected]
Andrea Giaccherini
Antonella Guerriero
ICCOM-CNR
[email protected]
[email protected]
Leonardo Guidoni
Sandro Jurinovich
Università degli Studi dell'Aquila
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
Műegyetem rkp. 3
via Selmi 2
1111, Budapest, Hungary
[email protected]
Alessandro Iagatti
LENS, INO-CNR
via Nello Carrara, 1
[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
Via Giovanni Gronchi 18 – Zona
industriale di Pile
67100, L'aquila, Italy
[email protected]
[email protected]
Fabio Invernizzi
Federico Locardi
Università degli Studi di Genova
Via Taramelli 16
27100, Pavia, Italy
[email protected]
VIA DODECANESO 31
16136, Genova, Italy
[email protected]
Mariangela Longhi
Simone Maranghi
Via Golgi 19
Via Aldo Moro, 2
53100, Siena, Italy
[email protected]
[email protected]
Michele Maggini
Mauro Marchetti
ICB-CNR
via Marzolo, 1
Traversa La Crucca 3 R. Baldinca LiPunti
07100, Sassari, Italy
[email protected]
[email protected]
Mirko Magni
Stefano Marchionna
RSE Spa, Ricerca sul sistema energetico
via Golgi 19
Via Rubattino 54
[email protected]
[email protected]
Francesco Malara
Giulia Marianetti
ISTM-CNR
Scuola Normale Superiore di Pisa
via Golgi 19
Piazza dei Cavalieri n°7
56017, Pisa, Italy
[email protected]
[email protected]
Norberto Manfredi
Alessio Masala
Università degli Studi di Milano-Bicocca
v. R. Cozzi 55
via G. Quarello 15/a
[email protected]
[email protected]
Jessica Manzi
Béla Matravolgyi
Budapest University of Technology and
Economics
v.le dell'Ateneo Lucano 10
[email protected]
Műegyetem rkp. 3
1111, Budapest, Hungary
[email protected]
Stouri Mbarek
Sara Morandi
ENSCM Chimie Montpellier
Università degli studi di Milano
11 rue Faubour Figurolles
Via Golgi 19
34070, Montpellier, France
[email protected]
[email protected]
Irene Mellone
Alessandro Mordini
ICCOM-CNR
ICCOM-CNR
via Madonna del Piano 10
[email protected]
[email protected]
Pietro Mendonca de Santis Sica
Adele Mucci
College of agriculture "Luiz de Queiroz"
Università degli S. di Modena e R.Emilia
Almirante Barroso Street, 338
via G. Campi 103
13416398, Piracicaba, Brazil
41125, Modena, Italy
[email protected]
[email protected]
Enzo Menna
Ana Belén Muñoz-García
Via Marzolo, 1
Federico II
Comp. Univ. Monte S. Angelo – Via
Cintia 26
[email protected]
Raluca Mereu
[email protected]
Dept of Material Science and
Marco Musiani
MIBSOLAR center , Via Cozzi 55
IENI-CNR
Corso Stati Uniti 4
[email protected]
[email protected]
Hamish Miller
CNR-ICCOM
Via Maddona del Piano 10
[email protected]
Piercarlo Mustarelli
via Marzolo, 1
[email protected]
Jijeesh Ravi Nair
Maria Pagliaro
Politecnico Di Torino
ICCOM-CNR
10129, TORINO, Italy
[email protected]
[email protected]
alberto Naldoni
CNR – ISTM
Via C. Golgi 19
20133, Milan, Italy
[email protected]
Gioele Pagot
via Gradenigo 6/a
[email protected]
Maria Assunta Navarra
Sapienza University of Rome
Monica Panigati
Piazzale Aldo Moro 5
185, Rome, Italy
Via Golgi, 19
[email protected]
[email protected]
Carlo Nervi
Fabiola Pantò
VIA P. GIURIA 7
Universita' Mediterranea di R. Calabria
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
via Selmi 2
[email protected]
Maria Cristina Paganini
via Giuria 7
Maria Laura Parisi
Via A. Moro 2
[email protected]
53100, Siena, Italy
[email protected]
Maurizio Passaponti
Emanuele Piciollo
Lem srl Socio Unico
via l. Valiani 55/59
52021, Levane - Bucine (AR), Italy
[email protected]
[email protected]
Carlo Pastore
Maddalena Pizzotti
CNR-IRSA (Istituto di Ricerca Sulle
Acque)
via Golgi 19
Viale De Blasio 5
70132, Bari, Italy
[email protected]
[email protected]
Andrea Pucci
Michele Pavone
Via Moruzzi 13
Federico II
56124, Pisa, Italy
COMP. UNIV. MSA VIA CINTIA 21
[email protected]
[email protected]
Elsa Quartapelle Procopio
Maurizio Peruzzini
via Golgi 19
ICCOM-CNR
[email protected]
[email protected]
Elena Rebollo
CNR-IENI
Rosaria Anna Picca
Corso Stati Uniti 4
Via. E. Orabona 4
[email protected]
70126, Bari, Italy
[email protected]
Gianna Reginato
ICCOM-CNR
[email protected]
Ilenia Rossetti
Nicola Sangiorgi
CNR-ISTEC
via C. Golgi 19
via Granarolo 64
[email protected]
[email protected]
Ruggero Rossi
Alessandra Sanson
CNR-ISTEC
viale Risorgimento 4
via Granarolo 64
[email protected]
[email protected]
Riccardo Ruffo
Saveria Santangelo
DICEAM, Università Mediterranea
via Cozzi 55
89122, Reggio Calabria, Italy
[email protected]
[email protected]
Caterina Sarno
Irene Ruggeri
Via Selmi 2
Università degli Studi di Roma Tor
Vergata
Via della Ricerca Scientifica 1
133, Roma, Italy
[email protected]
[email protected]
Francesca Russo
Elena Selli
via Golgi 19
[email protected]
Federica Sabuzi
Università degli Studi di Roma Tor
Vergata
via della Ricerca Scientifica
133, Rome, Italy
[email protected]
Adalgisa Sinicropi
Via A. Moro 2
53100, Siena, Italy
[email protected]
Stefania Siracusano
Valentina Toson
CNR-ITAE
Università del Piemonte Orientale
Via Salita Santa Lucia sopra Contesse, 5
VIA TERESA MICHELL 11
15121, Alessandria, Italy
[email protected]
[email protected]
Maurizio Taddei
Giulia Tuci
ICCOM-CNR
Via A. Moro 2
53100, Siena, Italy
[email protected]
[email protected]
Francesco Tassinari
Giovanni Valenti
Università degli S. di Modena e R.
Emilia
Via G. Campi 103
41100, Modena, Italy
Via Selmi 2
[email protected]
[email protected]
Federico Valerio
Cristina Tealdi
Viale Taramelli 12
27100, Pavia, Italy
Ordine Chimici Liguria
VIA MAZZINI 48/1,
Bogliasco (GE), Italy
[email protected]
[email protected]
Svetoslava Vankova
Maria Luisa Testa
CNR - ISMN
Via U. La Malfa 153
90146, Palermo, Italy
DISAT, Politecnico di Torino
corso Duca degli Abruzzi 24
[email protected]
[email protected]
Anna Maria Venezia
Giuseppe Torzillo
CNR – ISE
ISMN-CNR
via Duca degli Abruzzi 2
via Madonna del piano, 10
Palermo, Italy
[email protected]
[email protected]
Lorenzo Veronese
Lorenzo Zani
ICCOM-CNR
via Golgi 19
[email protected]
[email protected]
Daniele Versaci
[email protected]
Alberto Visibile
Via Golgi 19
[email protected]
Francesco Vizza
ICCOM-CNR
[email protected]
Margret Wohlfahrt-Mehrens
ZSW – und Wasserstoff-Forschung
Helmholtzstrasse 8
D-89081, Ulm, Germany
[email protected]
Isabella Zama
DAUNIA SOLAR CELL
via Zuccherificio 10
48123, Mezzano, Italy
[email protected]
List of Authors | 160
Abate A.
OP25
Aricò A.S.
P02
Abbotto A.
OP54
P63
OP13
Armaroli N.
KN5
P13
Armiento L.
OP35
P80
Atanassov P.
P79
P47
Avolio R.
P02
OP53
Baglio V.
OP54
Agnoli S.
OP5
Baglio V.
P63
Agostiano A.
KN4
Baldini L.
OP22
Acciarri M.
OP47
OP49
Aguiar C.L.
Aguilera L.
Alberti S.
Alidoost M.
P25
Baldoli C.
P03
P49
Ballarin B.
P64
P50
Bandara T.
P71
P51
Bang Y.H.
P78
Baptista A.S.
P49
OP10
P26
P50
OP14
P51
Allieta M.
P54
Barbero N.
P04
Alonso-Vante N.
KN6
Barbieri G.
OP21
OP14
Baricco M.
P48
P67
Barison S.
OP9
P01
Barolo C.
OP37
Amici J.
Angioni S.
P17
Antonucci P.
P04
OP6
Baroncini M.
OP20
P60
Barone V.
OP39
Appetecchi G.B.
P53
Barzagli F.
P05
Aprano S.
P22
Arbizzani C.
OP2
Argazzi R.
P06
Basosi R.
OP31
P39
P46
P58
P62
P79
Battisti L.
P32
P23
Becerril V.S.
P27
P36
Becerril V.S.
P71
161 | List of Authors
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
Boldrini C.L.
P13
Bellini M.
P08
Boldrini S.
OP9
Beltram A.
OP1
Bolzoni A.
P03
Belviso S.
OP43
Bonaccorso F.
P28
Benazzi E.
P36
Beneventi D.
P30
Bonchio M.
Berretti E.
P09
Bonchio .
KN1
P10
Boni A.
P73
Bertasi F.
OP43
OP17
OP46
OP17
P11
P57
P56
Bordiga S.
P78
Borsacchi S.
OP29
Borzatta V.
OP35
OP53
OP23
P48
Bessi M.
P72
Boshta M.
Bettucci O.
P71
Bossi A.
P03
Biagiotti G.
P24
Bossola F.
P14
Bianco S.
P07
Boutsika L.G.
Bignozzi C.A.
Bigoni F.
OP44
OP25
Brandiele R.
OP33
Breglia R.
OP11
OP45
Brown T.M.
OP43
P23
Brunetti A.
OP21
P36
Bruni G.
OP2
P15
P01
P65
Bruschi M.B.
Brutti S.
OP11
Caratto V.
P26
OP4
Caravella A.
OP21
P16
Carboni M.
OP4
P45
Cargnello M.
P24
Carlà F.
P31
Cacciarini M.
OP24
Carli S.
OP25
Calabrese V.
P80
Bussotti L.
Calamante M.
OP31
P27
P36
Carraro F.
OP5
Carvalho E.M.
P49
P35
P62
P50
Carvalho R.S.
P71
P72
Calegari R.P.
OP17
P49
P50
Casaluci S.
P49
P28
OP43
P50
Casarin L.
P36
Calvillo L.
OP5
Cattaneo A.S.
P17
Campagna S.
KN3
Cattelan M.
OP5
Cannavaro I.
P30
Cavallini M.
P21
Capasso A.
Capolupo F.
OP43
Cavina M.
OP38
P09
Cecconi B.
OP13
P21
P80
P31
Celi L.
P32
Caporali S.
P10
Cernuschi F.
P47
Capozzi M.A.
P18
Charalambopoulou G.
Caprasecca S.
OP18
Capriati V.
OP44
Chaussy D.
P30
P24
Chiarello G.
P75
P13
Ciasca C.V.
P18
Capriccioli A.
OP26
Cicchi S.
P24
Caramori S.
OP25
Cigarini L.
P33
OP33
Cimino S.
OP34
OP45
OP3
P23
OP51
P36
Cioffi N.
OP51
Dal Santo V.
OP1
P09
P14
P31
P52
Cipolla M.P.
OP33
P54
Colantoni I.
OP16
P60
Coletti G.
P12
P44
Colò F.
AL
Das K.C.
P51
P19
De Gioia L.D.
OP11
Colombo A.
OP33
De Giorgio F.
OP2
Compagnoni M.
OP32
P39
P20
Dekel D.R.
OP40
P09
Delgado Jaen J.J.
OP1
P21
Della Volpe C.
P32
Conte V.
P59
Delpeuch A.B.
OP46
Correa Baena J.P.
OP25
P11
Costa G.A.
P26
P78
Costantino F.
OP15
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
d’Ippolito G.
OP30
OP40
d’Ischia M.
P22
OP51
D'Acapito F.
OP16
P21
P34
P31
P23
P34
Comparini A.
Dalle Carbonare N.
P34
P09
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
Fantini S.
P53
P35
Fan Y.
OP6
P72
Farinola G.M.
KN4
Di Mauro A.E.
OP49
OP47
Di Michele A.
P20
P18
Di Noto V.
OP46
Faroldi F.
P11
Dipaquale L.
OP22
P25
P56
Fasoli M.
P26
P78
Fedeli S.
P24
OP30
Fedriguccia A.
OP38
Doglione R.
P68
Felici R.
P31
Doria S.
P35
Ferrara C.
P17
Dozzi M.V.
P75
P65
Dragonetti C.
OP33
Ferretti M.
P26
Drioli E.
OP21
Filippi J.
P08
Dulio S.
P37
Fino V.
P18
Durante C.
P15
Fiore A.
P18
OP50
Fiorilli S.
P19
Durrant J.R.
PL01
Floris B.
P59
Elamin K.
OP10
Focarete M.L.
P39
Elm J.
OP24
Foggi P.
P24
Enotiadis A.
OP44
P35
Errico M.E.
P02
P72
Escolástico S.
OP9
Folegatti V.
P12
Escorihuela S.
OP9
Folliero M.G.
P08
Ezzedine S.
P77
Fontana A.
OP30
Fontanesi C.
P33
Fornasiero P.
P73
OP16
OP1
OP51
OP13
P10
OP17
P31
P80
P33
P27
P34
Franchi D.
P35
Francia C.
OP14
P70
Franco F.
Frontera P.
Furlani M.
Głowacki E.D.
Galliano S.
Galloni P.
Gatti T.
Giannuzzi R.
P55
OP33
P55
OP6
Giorno L.
OP21
P60
Giurlani W.
P34
P27
Gobetto R.
OP28
P71
Gonsalvi L.
OP23
KN4
Gorni G.
OP35
OP37
Grądzka E.
P15
P04
Gräetzel M.
OP25
P59
Granozzi G.
OP5
OP27
P15
P28
OP50
Gatto I.
OP54
Gerbaldi C.
Giamello E.
OP48
Gionco C.
P59
Geppi M.
Giambastiani G.
P21
OP28
Gatto E.
Gennaro A.
Giaccherini A.
P15
Grätzel M.
Greco C.
Griffini G.
OP50
Guerriero A.
OP29
Guidoni L.
AL
Hagfeldt A.
AL
OP11
AL
OP23
OP7
AL
OP37
OP25
P07
P69
P19
PL02
P29
P30
P53
Hergert T.
P74
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
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.
OP24
Mari C.M.
OP8
Milano F.
OP47
Marrani A.G.
OP4
Martelli C.
OP35
Martini F.
OP29
KN4
Miller H.A.
OP40
P08
Martini M.
P26
Millia L.
P01
Martinuzzi S.
P10
Minarini C.
P22
Marzoratia S.
OP42
Minei P.
OP29
OP39
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
Monini M.
P35
Montegrossi G.
Montini T.
Nair J.R.
P53
P72
AL
OP16
P19
P31
P29
P34
P30
P73
Najafib L.
OP43
OP1
Naldoni A.
OP1
OP13
P52
P80
P54
Morandi S.
P52
P60
Mordini A.
OP31
P44
P27
Nastasi F.
KN3
P62
Navarra M.A.
OP10
P71
Nawn G.
OP46
P72
P11
P74
P56
Moreno M.
P53
P78
Mortalò C.
OP9
Morvillo P.
OP41
P11
Moukheiber E.
P63
P56
Mróz M.M.
OP1
P78
Mucci A.
OP41
P64
Muñoz-García A.B.
Musiani M.
OP12
OP3
Negro E.
Nelli I.
OP46
P26
Nencini L.
OP28
Nervi C.
OP28
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
Pezzella A.
P22
P69
Picca R.A.
OP51
OP6
P31
P60
P09
OP17
Picelli L.
P57
Piciollo E.
P73
Pignataro B.
P32
Pinna N.
OP50
P21
OP27
OP6
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
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
Tresso E.
P07
P58
Trevizan A.
P49
P79
Trevizan A.
P50
Triolo C.
P54
Sottile M.
OP29
Sportelli M.C.
OP51
P31
Stassi A.
Stelitano S.
OP54
OP6
Touloupakis E.
OP36
P60
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
173 | NOTES
NOTES | 174
175 | NOTES
NOTES | 176
177 | NOTES

BOOK OF ABSTRACT - ENERCHEM-1

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