Community Research and Development Information Service - CORDIS

FP7

ArtipHyction Report Summary

Project ID: 303435
Funded under: FP7-JTI
Country: Italy

Final Report Summary - ARTIPHYCTION (Fully artificial photo-electrochemical device for low temperature hydrogen production)

Executive Summary:
The time has indeed come to establish an extensive research effort to develop concepts and technologies to exploit the enormous amount of solar energy, which falls on our planet. The annual global energy consumption rate at present is about 16 TW and will rise towards 20 TW within this decade. The energy provided by solar radiation is over 100,000 TW. At present about 11 % of global fuel demand comes from biomass (combustion and fermentation) while 85% is derived from fossil fuels. In terms of solar energy conversion, the early stages of photosynthesis, including the water splitting reaction, are highly efficient, while the production of biomass is much less so. The ArtipHyction (PEC) technology is aimed at carrying out water splitting to get directly purified H2 in an intensified system compared to that taking place naturally in algae and, therefore, has the potential to solve the problem of energy procurement of mankind and to have an impact much broader than those hypothesised now for biofuels.
The ArtipHyction project let the FCH JU initiative become a key player in the worldwide PEC R&D context. For this reason, a Science Policy Brief was produced by a consortium of European Scientists, for the European Science Foundation entitled “Harnessing Solar Energy for the Production of Clean Fuel”. The mission of the ArtipHyction project followed this path by gathering together scientists with clear expertise and a wide former cooperation record from the fields of physical chemistry, organic chemistry, biochemistry, molecular biology, material sciences and chemical engineering. Coupled to this interdisciplinary team is the involvement of high-technology SMEs selected for their unique capabilities and strong commitment.
In line with the reference Annual Implementation Plan of the FCH JU, the Artiphyction concept is a promising sustainable technology for the production of green H2 at low temperatures where the whole production chain is limited in a PEC cell, which on the one hand collects the sunlight and on the other hand produces in situ continuous hydrogen and oxygen. The project has successfully implemented the scale up of the technology from a 1.5 cm2 (of photoactive area) in a lab-scale cell to the 1.6 m2 prototype, overcoming the drawbacks and collecting experience from four successive dimension upgrades. Nevertheless, high troubles were faced for the scale up of the lab results, regarding mostly the electrodes performance and the device design. Therefore, even though efficiencies as high as 5% have been achieved with small photo-electrodes (1.5 cm2 of photoactive area) in lab tests, the scale-up of the electrodes (each of 64 cm2 of photo-active area) induces additional losses that compromise their efficiency. Moreover, in the final device the efficiency must account not only the photoactive area, but the actual area covered by the prototype, and such leads to a decrease in about a half of the overall current density values. For such reason, as well as due to the choice of mitigate the stressed conditions of the maximum efficiency working point operating at a lower current density in favour of a prolonged lifetime of the PEC cells, the final Artiphyction prototype worked with an efficiency of about 1% and is able to achieve up to 3% (producing from 1 to 2 g/h H2), with a proved stability of 1.000 h.
Furthermore, the project achieved a significant result in term of demonstration at practical application size (1.6 m2), bringing out of the labs the technology to be evaluated in real environment up to a TRL 5, which was previously missing for the PEC H2 production technology.
As natural, several opportunities to increase performance and, most of others, to drastically reduce the production cost were advised from a complete techno-economic analysis of the developed technology. The chance to enlarge the size of the prototype unit, and consequently increase the production volumes of cells and panels, will generate more experience and will drive the cost reduction, taking advantage of bigger purchasing and serialised machining and operation.
Overall, the main objective of future exploitation works after the completion of the ArtipHyction project is to create a significant and practical PEC technology in the medium long term, to create awareness of its potential benefits, to assess how the reduction of the production cost versus the increase on production volumes can facilitate the profitability of large-scale sun-driven H2 production. From the previously presented analysis, a scale up to 10 m2 of the PEC device is practically the next step that should be followed, in order to render economically feasible the H2 production with the photo-electrochemical technology used in the Artiphyction project. Obviously, more efforts are necessary to increase the current efficiencies at values higher than 5 %. From the analysis made based on the Artiphyction prototype, the H2 production cost can reach lower values than 5 €/kg in less than 5 years, if the device efficiency is higher than 10% (while for lower efficiency values the fixed costs must be drastically reduced), thus making the Artiphyction technology competitive in the current green H2 production market.

Project Context and Objectives:
Leaves can split water into O2 and H2 at ambient conditions exploiting sun light. James Barber, one of the key players of ArtipHyction, elucidated Photosystem II (PSII), the enzyme that governs this process. In photosynthesis, H2 is used to reduce CO2 and give rise to the various organic compounds needed by the organisms or even oily compounds which can be used as fuels. However, a specific enzyme, hydrogenase, may lead to non-negligible H2 formation even within natural systems.
Building on the pioneering work performed in a FET project based on natural enzymes and the convergence of the work of the physics, materials scientists, chemical engineers and chemists involved in the project, an artificial device will be developed to convert sun energy into H2 with close to 10% efficiency by water splitting at ambient temperature, including: i) an electrode exposed to sunlight carrying a PSII-like chemical mimic deposited upon a suitable transparent electron-conductive porous electrode material (e.g. ITO, FTO); ii) a membrane enabling transport of protons via a pulsated thin water gap; iii) an external wire for electron conduction between electrodes; iv) a cathode carrying an hydrogenase-enzyme mimic over a porous electron-conducting support in order to recombine protons and electrons into pure molecular hydrogen at the opposite side of the membrane.
A tandem system of sensitizers will be developed at opposite sides of the membrane in order to capture light at different wavelengths so as to boost the electrons potential at the anode for water splitting purposes and to inject electrons at a sufficiently high potential for effective H2 evolution at the cathode. Along with this, the achievement of the highest transparence level of the membrane and the electrodes will be a clear focus of the R&D work. The main goal of the project is to develop a proof of concept prototype of about 100 W (3 g/h H2 equivalent with a projected lifetime of >10.000 h) that will be assembled and tested by the end of the project for at least 1000 h.
The work in this third reporting period of the project is in line with expectations. However, to further increase the chances of success a new back-up solution has been conceived by the partnership including the use of photovoltaic cells occupying the no-utilize space in the external surface of the housing so as to boost electron potential and achieve H2 evolution with no need of external bias. The development of this concept was carried out in the third year of the project, when the design of the prototype evolved and it was developed a modular and compact design with a total of 1.6 m2 of occupied area.

Project Results:
A more detailed description of the work done in the second reporting period is provided in the attached to Final Report of the project.

The main achieved RESULTS are put in relationship with respect to the original concept and OBJECTIVES (OB) of the project:

OB1: Targeted minimum efficiency exceeding 5% solar energy to hydrogen heating value
Antenna systems at the anode and the cathode will be tailored in order to exploit higher energy photons (e.g. wavelengths below 600 nm) at the anode, where the water-splitting occurs, and the lower-energy ones (wavelengths above 600 nm) at the cathode where proton reduction takes place. Model calculations, presented in the impact section, show that this con¬cept has the potential to exceed 10% conversion efficiencies, which would offset the competition of combined commercial photovoltaic panels and water electrolysers.

RESULT of OB1: Partially achieved
• The best results with a CoPi-catalysed Mo-doped BiVO4 photo-anode and a Co NPs-based cathodic electro-catalyst in the Final Artiphyction prototype show a potential of 3% overall sunlight into hydrogen conversion efficiency, however, due to mass-transfer and kinetics limitations phenomena (bubbles formation and accumulation in the electrodes surface) the performance decrease up to about 2% during long term operation (see D1.5 and D6.3).
• This paves the way to full achievement of the ambitious goal of the project by: more engineering efforts on reactor design to improve fluidodynamics (although already 4 different versions of prototype device have already evolved during the Artiphyction project); and a further optimization on electroactive materials.
• Detailed modelling data are pointing at the way to go (D7.5 and D1.5) with the measured performances and show that 10% conversion is quite compatible with thermodynamic calculations but requires the development of appropriate electrocatalytic micro- and nano-structures.

OB2: The prospected system durability will exceed 10.000 h lifetime. The final prototype will be tested for at least 1000 h in the last six months of the project.

RESULT of OB2: Partially achieved
• The final prototype module of 5 PEC-PV units has been tested for 1000h and a limited reduction of efficiency (less than 5%) has been observed when operating at a 2% STH efficiency. Indeed, a trade-off between STH efficiency and stable operation has been pointed out (see D6.3) in order to maintain the stability with the prospective durability of 10.000 h.

OB3: To disclose wide potential application opportunities, the above targets must be reached without using expen¬sive noble metals or materials and via assembling techniques amenable for mass production.

RESULT of OB3: Achieved
Attention have been addressed mostly on the anode water-splitting side of the cell were noble metal catalysts are not present. The synthesis techniques adopted for BiVO4 and Co-based catalysts are amenable for mass production and were actually used to manufacture the final Artiphyction prototype.

OB4: The system can be modular and reach whatever production goal in the range from 100 W for domestic use (ca. 3 g/h H2 equivalent) up to 100 kW (ca. 3 kg/h H2 equivalent) for commercial use. By the end of the project a proof-of-concept prototype for domestic use (3 g/h H2 equiva¬lent) will be engineered, assembled and tested.

RESULT of OB4: Partially achieved
Special attention was paid on manufacture a modular system. The final ARTIPHYCTION prototype is composed of 20 modules, each of them with 5 PEC-PV units that can be assembled to reach different total areas. The original module surface area has been achieved. However, even though the system was proved to be able to operate at 3% of STH efficiency, a strategic decision was taken in favour of the prototype stability. Hence, a half of the possible PV cells were used in the system, since in this case the stability would prevails (with a 5% of margin) although the activity of the PEC cells would decrease of 25%. Therefore, the maximum overall H2 production of the prototype is slightly higher than 1 g/h.

The main results obtained so far are here listed on a WorkPackage basis.

WP 1000. Coordination and management (Resp.: POLITO)
- Web site opened (Deliverable 1.1)
- Dissemination plan issued (Deliverable 1.2)
- 12 month project review accomplished (Deliverable 1.3)
- Revision of ArtipHyction concept managed (see Appendix 1 in Deliverable 1.6)
- Numerous papers and conference presentations were delivered (see Deliverable 1.7)

WP 2000. Light-driven water splitting catalysts (Resp.: POLITO)
- TiO2 and BiVO4 catalysts developed for <= 600 nm photons absorption and exploitation
- BiVO4 catalyst selected for its higher durability potential
- deposition of BiVO4 layers on TCO electrodes undertaken with promising results and numerous
techniques (dip coating, spin-coating, screen-Printing; see deliverables 2.1, 2.2 and 5.1)
- water splitting performance achieved is currently compatible with 5% of the final sun-to-hydrogen
conversion efficiency target
- scale-up of BiVO4-based photo-electrodes from 1.5 cm2 to 100 cm2 was accomplished, however, although the performance of the higher size photo-anodes under current-potential curves was similar, the performance of the bigger electrode under continuous applied bias decreased up to 5 times due to higher carriers recombination caused by the worse electrons transport in the BiVO4 electrode, among another possible reasons.

WP 3000. Hydrogen evolution mimic (Resp.: CEA)
- The cobalt diimine dioxime complexes identified as most promising hydrogenase mimics
- Sensitizer developed based on a donor part (triphenyl-amine), an acceptor part (naphtalimide) and
the Pi-linkage between them (bithiophene), which also has the role of absorbing light.
- The research carried out to tether catalyst sensitizer and TCO electrode showed insufficient specific activity per unit electrode area. However, the molecular cobalt-based catalysts have been benchmarked and compare well with other synthetic catalysts and hydrogenase enzymes.
- Non-photocatalytic Co-based H2 evolution show particular promise providing a catalytic activity equal to Pt. Successful grafting of molecular and electrodeposited Co-based H2-evolving catalysts was achieved on nanostructured NiO and AZO substrates. This last catalyst will be incorporated in the final prototype.
- Due to the decision of operating the final device with a gas diffusion electrode, it was developed to synthesize Co NPs onto the surface of a GDL for its subsequent transformation on the Co-H2-catalyst under electrochemical conditions.

WP 4000. Electrodes structural materials (Resp.: TECNAN)
- Porous coatings were obtained from TCOs by screen printing and thermal spraying. Transparent layers were obtained from TCOs prepared by screen printing in the case of AZO and FTO (see Deliverables 4.1 and 4.2). Best results were obtained with FTO. However, all the synthesised TCO porous materials looks to have a high resistance once deposited, in the order of kΩ cm. In the case of FTO, lower resistivity of nanoparticles has been obtained, however porosity in the deposition will affect negatively to the conductivity being these two properties not compatible.
- Taking into account the conclusions of the characterisations made as well as input provided from work in WP1 and WP2, it has been proposed to select FTO as TCO material. ITO was discarded mainly by economic reasons and AZO was discarded as it reacts in acid medium during the preparation of the BiVO4 photoactive film.
- Taking into account the low conductivity of the FTO due to porosity, it was decided to use FTO-glass coated by Solaronix through CVD technique (having only 7 Ω cm2 of resistivity) for the anodic electrodes of the final Artiphyction prototype (see Deliverable 4.2).

WP 5000. Electrodes development (Resp.: PYRO)
- Porous electrodes were synthesized based on the transparent conducting oxides powders developed in WP4000 and on the design guidelines derived from WP7000. Three techniques were considered to boost the chances of success:
-) thermal spray (a technique lying in the expertise of PYRO) in ceramic substrates for the manufacturing of self-standing electrodes with controlled porosity.
-) screen printing (a technique used by SLX for their DSC cells development) for the development of transparent electrods supported on glass (see D4.2).
-) Thermal CVD (commercial process of Solaronix for producing low resistivity FTO)
Within the second project year FTO, ITO and AZO coated electrodes have been developed based on optimized powders of such TCO. However, among all the prepared samples, the most promising for the final Artiphyction prototype have been individuated to be the FTO/glass electrodes prepared by thermal CVD, due to their highest conductivity, transparency and stability.
- Photoanodes consisting of Co-Pi deposited on a Mo-BiVO4 film, reported the best photo-activity within all the studied materials.
- It was developed a test-rig where electrolyte pulsation can be accomplished at different frequencies and intensities. This setup has been thoroughly described in deliverable Deliverable 5.1. During specific tests, pulsation was found to be able to significantly increase the electrolysis yield with over 10% reduction of electrode potentials.

WP6000: Design, construction and testing of ArtipHyction prototype (Resp. HST)
- The final Artiphyction prototype was designed, optimized, manufactured and tested. Long-term (1.000 h) was completed with a loss on the activity of less than 5 %, as more detailed in the final report on performance and stability tests (Deliverable 6.3). From such result, it is possible to affirm that the final Artiphyction prototype is able of work under at least 1000 h (of proved operation) with a mean overall current of 19.2 A (~12 A/m2), with a corresponding efficiency close to 2% and a H2 productivity of about 1 g/h, with the current used number of PVs. It is necessary to consider that working with the double of the PVs, which actually can be put in the case of the prototype, it will be possible to achieve 3% of efficiency, and about 1.5 g/h of H2. In addition, if the electrodes on the current prototype are substituted for more efficient ones, it should be possible to achieve even higher H2 productivities.

WP7000. Modelling, LCA and energy scenarios studies (Resp. CPERI)
- An accurate reproduction of effects of water pulsation on electrode layers was performed. Detailed flow simulations of TCO membranes developed within the ArtipHyction project. Simulation results are summarized in Deliverable 1.6. Infiltration appears to occur in abrupt bursts as the pressure to overcome stenosis in the membrane is reached.
- The models developed at POLITO provide useful tools to determine and compare important parameters affecting the photo-catalytic and electro-catalytic performance of the electrodes and the final efficiency of the PEM photo-electrolyzer (see Deliverable 7.1 to Deliverable 7.4).
- LCA and techno-economic analysis were performed based on the outcomes of the project and the final manufactured prototype.
- The study on the potential future penetration of the ArtipHyction technology was also performed (see Deliverable 7.5). Overall, the main objective of future exploitation works after the completion of the ArtipHyction project will be to create a significant and practical PEC technology in the medium long term, to create awareness of its potential benefits, to assess how the reduction of the production cost versus the increase on production volumes can facilitate the profitability of large-scale sun-driven H2 production. From the analysis reported in Deliverable 7.5, a scale up to 10 m2 of the PEC device is practically the next step that should be followed, in order to render economically feasible the H2 production with the photo-electrochemical technology used in the Artiphyction project. Obviously, more efforts are necessary to increase the current efficiencies at values higher than 5 %. From the analysis made based on the Artiphyction prototype, the H2 production cost can reach lower values than 5 €/kg in less than 5 years, if the device efficiency is higher than 10% (while for lower efficiency values the fixed costs must be drastically reduced), thus making the Artiphyction technology competitive in the current green H2 production market.
Potential Impact:
The Artiphyction project has successfully implemented the scale up of the PEC H2 production technology from a 1.5 cm2 (of photoactive area) in a lab-scale cell to the 1.6 m2 prototype, overcoming the drawbacks and collecting experience from four successive dimension upgrades. Nevertheless, high troubles were faced for the scale up of the lab results, regarding mostly the electrodes performance and the device design. Therefore, even though efficiencies as high as 5% have been achieved with small photo-electrodes (1.5 cm2 of photoactive area) in lab tests, the scale-up of the electrodes (each of 64 cm2 of photo-active area) induces additional losses that compromise their efficiency. Moreover, in the final device the efficiency must account not only the photoactive area, but the actual area covered by the prototype, and such leads to a decrease in about a half of the overall current density values. For such reason, as well as due to the choice of mitigate the stressed conditions of the maximum efficiency working point operating at a lower current density in favour of a prolonged lifetime of the cells, the final Artiphyction prototype worked with an efficiency of about 1% and is able to achieve up to 3% (producing from 1 to 2 g/h H2), with a proved stability of 1.000 h.
Overall, the main objective of future exploitation works after the completion of the ArtipHyction project is to create a significant and practical PEC technology in the medium long term, to create awareness of its potential benefits, to assess how the reduction of the production cost versus the increase on production volumes can facilitate the profitability of large-scale sun-driven H2 production. From the previously presented analysis, a scale up to 10 m2 of the PEC device is practically the next step that should be followed, in order to render economically feasible the H2 production with the photo-electrochemical technology used in the Artiphyction project. Obviously, more efforts are necessary to increase the current efficiencies at values higher than 5 %. From the analysis made based on the Artiphyction prototype, the H2 production cost can reach lower values than 5 €/kg in less than 5 years, if the device efficiency is higher than 10% (while for lower efficiency values the fixed costs must be drastically reduced), thus making the Artiphyction technology competitive in the current green H2 production market.
With a solar light to hydrogen conversion efficiency of 10 % and an average solar radiation input of 1000 kWh per m2 in Europe, one gets 3 kg of solar H2 per year per m2 of exposed PEC converter surface. If a 7 €/kg cost of solar-electrolytic hydrogen is considered, each single panel will provide an equivalent H2 value of about 24 €/m2/yr. Assuming a lifetime of 20 years of the ArtipHyction panels (i.e. a depreciation of 5 % p.a.), and a money capitalization of 5 %, one can afford costs lower than 200 €/m2 of the ArtipHyction panels including the installation.
When comparing the projected dye solar cell module costs of ~ 80 € / m2 (taken on a 20 MWp/year we may assume that the ArtipHyction panels could cost no more than 100 € /m2, still leaving up to 100 € /m2 for installation and hydrogen handling.
With scaling-up and the rational production of the hydrogen handling parts, overall costs of less than 100 € per installed m2 are achievable, opening a huge market of clean hydrogen fuel, being cheaper than today’s fossil fuels. PEC technology can generally produce hydrogen in local, semi-central, and central settings and has a chance to reach hydrogen production costs levels comparable to water electrolysis and steam methane reforming by 2030.
As described in the “Study on hydrogen from renewable resources in the EU” by Ludwig-Boelkow-Systemtechnik GmbH, PEC technologies need to increase experience on larger-scale system, to increase the actual TRL to better compete and potentially win the race for an affordable Hydrogen Production Cost with renewable energy. The Artiphyction project achieved a significant result in term of demonstration of H2 production at a practical application size (1.6 m2) in a PEC system, bringing out of the labs the technology to be evaluated in real environment that correspond to a TRL 5.
From the gaps analysis benchmarking the key performance indicators (KPI) of six selected path ways against water electrolysis (WE) and steam methane reforming (SMR) for the reference year 2030, in the above mentioned study, it is possible to verify how the scale-up of the Artiphyction technology (and a consequent improvement on efficiency, optimized materials, reactor design, lifetime, cost-reduction, integration with another devices such as PV or concentrated PV cells, etc) can lead to the improvement of the most critical key performance indicators of the PEC technology (i.e. TRL and H2 cost).
The PEC technology offers one of the most interesting (and challenging) pathways for hydrogen production as it offers the theoretical prospect of being only slightly more complex than pure PV technology at only marginally higher cost. The long-term target for the PEC hydrogen production pathway is to reach efficiencies comparable to those of PV combined with electrolysis using cost competitive materials. Hence, research should aim to achieve solar-to-hydrogen efficiencies in the range of at least 10% to 12% while ensuring device stability and minimum degradation for a period of at least 10 years. Those conditions could lead to hydrogen production costs in the range of 4-5 €/kgH2 by 2030. R&D efforts should focus on materials development, along with reactor design and engineering. As natural, several opportunities to increase performance and, most of others, to drastically reduce the production cost were advised from a complete techno-economic analysis of the developed technology. The chance to enlarge the size of the prototype unit, and consequently increase the production volumes of cells and panels, will generate more experience and will drive the cost reduction, taking advantage of bigger purchasing and serialised machining and operation. The work should hence be directed to improve the device efficiency and durability, while increasing systems size and decreasing its costs.
MAIN DISSEMINATION ACTIVITIES:

Training Events
A training event on “Future and Zero Carbon Energy” was held on 25 June 2015 at CERTH location in Thessaloniki, Greece in the frame of Artiphyction project.

Publications
1. Martinez Suarez C., Hernández S., Russo N., “BiVO4 as photocatalyst for solar fuels production through water splitting: A short review”, Applied Catalysis A: General, 2015, 504, 158-170.
2. Nicolas Queyriaux, Nicolas Kaeffer, Adina Morozan, Murielle Chavarot-Kerlidou,Vincent Artero∗, “Molecular cathode and photocathode materials for hydrogen evolution in photoelectrochemical devices”, J. Photochem. Photobiol. C, 2015 25, 90-105.
3. C. J. Wood, G. H. Summers, C. Clark, N.Kaeffer, M.Brautigam, L. Roberta Carbone, L. D'Amario,K. Fan, Y. Farré, S. Narbey, F. Oswald, L. A. Stevens, M. R. Hall, C. E. Snape, B. Dietzek, D. Dini, L. Hammarström, Y. Pellegrin, F. Odobel, L. Sun, V. Artero, E. A. Gibson*, “A comprehensive comparison of dye-sensitized NiO photocathodes for solar energy conversion”, Phys. Chem. Chem. Phys. 2016.
4. N. Kaeffer, A. Morozan, V. Artero*,“Oxygen Tolerance of a Molecular Engineered Cathode for Hydrogen Evolution Based on a Cobalt Diimine–Dioxime Catalyst”, J Phys. Chem. B, 2015.
5. C. Ottone, M. Armandi, S. Hernández, S. Bensaid, M. Fontana, C. F. Pirri, G. Saracco, E. Garrone and B. Bonelli, “Effect of surface area on the rate of photocatalytic water oxidation as promoted by different manganese oxides”, Chemical Engineering Journal, 2015, 119, 13707-13.
6. D. Hidalgo, S. Bocchini, M. Fontana, G. Saracco and S. Hernandez, “Green and low-cost synthesis of PANI-TiO2 nanocomposite mesoporous films for photoelectrochemical water splitting”, RSC Advances, 2015, 5, 49429-49438.
7. S. Hernandez, D. Hidalgo, A. Sacco, A. Chiodoni, A. Lamberti, V. Cauda, E. Tresso and G. Saracco, “Comparison of photocatalytic and transport properties of TiO2 and ZnO nanostructures for solar-driven water splitting”, Physical Chemistry Chemical Physics, 2015, 17, 7775-7786.
8. S. Hernández, G. Barbero, G. Saracco and A. L. Alexe-Ionescu, “Considerations on Oxygen Bubble Formation and Evolution on BiVO4 Porous Anodes Used in Water Splitting Photoelectrochemical Cells”, The Journal of Physical Chemistry C, 2015, 119, 9916-9925.
9. D. Hidalgo, R. Messina, A. Sacco, D. Manfredi, S. Vankova, E. Garrone, G. Saracco and S. Hernández, “Thick mesoporous TiO2 films through a sol–gel method involving a non-ionic surfactant: Characterization and enhanced performance for water photo-electrolysis”, International Journal of Hydrogen Energy, 2014, 39, 21512–21522.
10. S. Hernández, M. Tortello, A. Sacco, M. Quaglio, T. Meyer, S. Bianco, G. Saracco, C. F. Pirri and E. Tresso, “New Transparent Laser-Drilled Fluorine-doped Tin Oxide covered Quartz Electrodes for Photo-Electrochemical Water Splitting”, Electrochimica Acta, 2014, 131, 184-194.
11. Hernández S, Thalluri SM, Sacco A, Bensaid S, Saracco G, Russo N. “Photo-catalytic activity of BiVO4 thin-film electrodes for solar-driven water splitting”. Applied Catalysis A: General. 2015, 504, 266-271.
12. Vincent Artero, Jean-Michel Savéant, Toward the Rational Benchmarking of Homogeneous H2-Evolving Catalysts, submitted to Energy Environ. Sci. (2014)
13. Bhattacharjee, E. S. Andréiadis, M. Chavarot-Kerlidou, M. Fontecave, M. J. Field*, V. Artero*, A Computational Study of the Mechanism of Hydrogen Evolution by Cobalt(Diimine-Dioxime) Catalysts, Chem. Eur. J. 2013, 19, 15166 – 15174.

Oral Communications at International Conferences/Workshops:
1. N. Kaeffer, R. Brisse, J. Massin, A. Morozan, C. Windle, B. Jousselme, M. Chavarot-Kerlidou, V. Artero "Toward the construction of fully molecular photocathodes for hydrogen evolution" Gordon Research Seminar on Renewable Energy: Solar Fuels 27-28 February 2016, Borgo, Italy
2. Hernández S., Russo N., Saracco, G. (Invited Talk), “Development of BiVO4-based photoanodes for a sun-driven water-splitting device”, Energy Materials Nanotechnologies (EMN) Meeting on Photocatalysis, 21-24 November 2015, Las Vegas, USA.
3. Hernández S., Bensaid S., Russo N., Saracco, G., “Comparison of catalytic and photocatalytic water oxidation materials through the reaction kinetics in a three-phases bubbling reactor”, European Meeting on Environmental Chemistry (EMEC16), 30 November – 3 December, 2015, Turin, Italy. http://www.emec16.com/index.php Hernández S., Bensaid S., Ottone C., Thalluri M.S., Armandi M., Bonelli B., Russo N., Garrone E., Saracco G. “Comparison of catalytic and photocatalytic water oxidation materials through the reaction kinetics in a three-phases bubbling reactor”, Catalysis for Renewable Sources: fuel, energy, chemicals, September 6-11, 2015, Catania, Sicily, Italy. http://conf.nsc.ru/CRS3 R. Brisse, N. Kaeffer, V. Artero, B. Geffroy, T. Gustavsson and B. Jousselme, “Ink-jet printing NiO for efficient p-type and tandem DSSC: An illustration through a yellow to blue series of new push-pull dyes“, SCF 2015- Lille (France), 4 - 9 july 2015.
4. T. Bourgeteau, D. Tondelier, B. Geffroy, V. Artero, B. Jousselme “Photocathodes based on organic semiconductors coupled to a MoS3 catalyst for solar hydrogen production“, 24 April-1 May 2015, International Solar Fuel conference (ISF-1 Young satellite meeting), Uppsala, Sweden
5. T. Bourgeteau, B. Geffroy, D. Tondelier, V. Artero, B. Jousselme. “Photocathodes based on organic semiconductors coupled to a MoS3 catalyst for solar hydrogen production“, Oral, Conférence National, Science et Technology des Systèmes pi-Conjuguès (SPIC), Angers, 12-16/10/2015.
6. B. Jousselme, (Invited talk), Photocathodes based on hybrid materials, Workshop on Future Low and Zero Carbon Energy, Thessaloniki – Greece – 25-26/06/2015.
7. T. Bourgeteau, B. Geffroy, D. Tondelier, V. Artero, B. Jousselme, “A H2-evolving photocathode based on P3HT-PCBM bulk heterojunction solar cells and a MoS3 catalyst“, Oral, Conférence Internationale, Solar Fuel 2015, Mallorca, Spain, 10-13/03/2015.
8. M. Vardavoulias, "Industrial thermal spray coatings for tribological applications. Influence of porosity and nanostructure on wear properties”, presented in TURKEYTRIB 15, 1st International Conference on Tribology 7-9 October 2015, Yildiz Technical University, Istanbul, TURKEY.
9. M. Vardavoulias, “Thermal spray applications in the food industry”, presented in the WORKSHOP “Chalenges in developing materials for improving process in oil and sugar production”, National Technical University Athens, GREECE, 6-8 May 2015.
10. N. Kaeffer, A. Morozan, M. Chavarot-Kerlidou, V. Artero, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, T.A. Moore, A. L. Moore, D. Gust, “Playing with (photo)cathodes based on cobalt diimine-dioxime complexes towards their integration in device - SOFI-fellow presentation” April 2015, 1st International Solar Fuels Conference: Young Meeting, Uppsala, Sweden.
11. M. Chavarot-Kerlidou, N. Queyriaux, N. Kaeffer, J. Massin, R. Jane, J. Fize, V. Artero, “Molecular strategy towards the construction of H2-evolving photocathodes for water splitting”, SCF’15 Chimie et Transition Energétique, 4 – 9 juillet 2015, Lille, France.
12. V. Artero (Invited talk), “Bioinspired catalytic systems and technological applications of hydrogen”, Pacifichem 2015, Honolulu, USA, 14-20 December 2015.
13. V. Artero (Invited talk), “Molecular H2-evolving catalysts with proton relays: Design, mechanistic studies, and benchmarking of catalytic activity”, 250th ACS meeting, Boston, USA, 16-20 August 2015
14. V. Artero (Invited talk), “Biomimetic, bioinspired and biosynthetic H2-evolving catalysts”, ICBIC XVII, Beijing, China, 20-24 July 2015.
15. V. Artero (Invited talk), “Molecular H2-evolving catalysts: design, benchmarking and system integration”, SFN workshop on "Solar Fuels: Moving from Materials to Devices", The Royal Society, London, UK, 7-8 July 2015.
16. V. Artero (Invited talk), “From bio-inspired catalysts for H2 evolution to photoelectrode materials”, ISF-1 First International conference on Solar fuels, Uppsala, Sweden, April 27- May 1, 2015.
17. Ottone C., Armandi M., Hernández S., Fontana M., Bensaid S., Garrone E., Bonelli B., “Actual rate of oxygen production of different manganese oxide phases as water oxidation catalysts”. 23rd International Symposium on Chemical Reaction Engineering (ISCRE 23), 7-10 September 2014, Bangkok, Thailand.
18. Hidalgo D., Sacco A., Lamberti A., Chiodoni A., Cauda V., Tresso E., Hernández S., “TiO2 and ZnO nanostructured photoelectrodes for solar-driven water splitting”, E-MRS Fall meeting, September 15-18, 2014, Warsaw, Poland.
19. Hernández S., Bensaid S., Ottone C., Armandi M., Fontana M., Bonelli B., Russo N., Pirri C.F., Saracco G., “Comparison of catalytic and photocatalytic water oxidation materials through the reaction kinetics in a three-phases bubbling reactor”, 9th international symposium on CAtalysis in MUltiphase Reactors (CAMURE 2014), December 7-10, Lyon , France. http://www.camure2014.fr.
20. V. Artero (Invited talk), “Molecular H2-evolving catalysts: design, benchmarking and system integration”, International Conference on Artificial Photosynthesis (ICARP2014), Awaji City (Hyogo), Japan, November 24-28th 2014.
21. V. Artero (Invited talk), “Hydrogen evolution: bioinspired catalysts and artificial hydrogenases”, Symposium on Bioinspired solar-energy conversion, 16th International Congress on Photobiology, Cordoba, Argentina, September 8-12th 2014.
22. Hernández, S. (Invited Seminar), Techniques for functional characterization of photocatalytic materials for Water Splitting, 16h seminar, TEDAT project at ENEA research center, Brindisi (IT), April 2014.
23. V. Artero (Invited talk), “Hydrogen evolution: bio-inspired catalysts and artificial hydrogenases”, EuCheMS Chemistry Congress (ECC5), Istanbul 31 August - 4 September 2014.
24. V. Artero (Invited), ”Hydrogen evolution: bio-inspired catalysts and artificial hydrogenases”, 12th European Biological Inorganic Chemistry Conference (EuroBIC-12), Zurich, Switzerland, 24-28 August 2014.
25. V. Artero (Invited talk), “Cobalt-based catalysts for hydrogen evolution” and “Molecular Catalysis for Water Oxidation and Reduction” Session at the 41st International Conference on Coordination Chemistry (ICCC-41), Singapore, 21-15 July 2014.
26. T. Bourgeteau, B. Geffroy, D. Tondelier, R. Brisse, C. Laberty-Robert, R. de Bettignies, V. Derycke, V. Artero, S. Palacin, B. Jousselme, “Direct photosensitization of MoS3 by polymer-fullerene bulk heterojunction solar cells for hydrogen photoproduction“, International Displays Research Workshop 2014 10th French-Korean Joint Workshop (Ecole Polytechnique / Kyung Hee University), 20-21 January 2014, Paris, France
27. T. Bourgeteau, D. Tondelier, T. Cabaret, B. Geffroy, V. Derycke, B. Jousselme, “Hybrid photocathodes for solar hydrogen production: organic photovoltaics as a sensitizer of catalysts for water reduction“, ElecMol, 25-29 August 2014, Strasbourg, France
28. V. Artero (Invited talk), “From bio-inspired catalysts for H2 evolution to photoelectrode materials”, Séminaire invité de l’institut de chimie de Catalogne (ICIQ), Tarragone, Spain, May 15 2015.
29. V. Artero, “Molecular H2-evolving catalysts: design, benchmarking and system integration”, International Conference on Artificial Photosynthesis (ICARP2014), Awaji City (Hyogo), Japan, November 24-28 2014.
30. N. Kaeffer, A. Morozan, M. Chavarot-Kerlidou, V. Artero, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, T.A. Moore, A. L. Moore, D. Gust, “Implementing molecular photo/catalytic components into an overall water-splitting tandem cell”, Perspect-H2O Supramolecular Photocatalytic Water Splitting COST Action CM1202, Joint Working Group Meeting of Working Groups 3 and 4, Lund, Sweden, October 02-04 2014.
31. V. Artero, “Toward the rational benchmarking of homogeneous H2-evolving catalysts” bimensual JCAP / SOFI videoconference, September 26 2014.
32. V. Artero, “Hydrogen evolution: bio-inspired catalysts and artificial hydrogenases”, 12th European Biological Inorganic Chemistry Conference (EuroBIC-12), Zurich, Switzerland, August 24-28 2014.
33. V. Artero, “Hydrogen and artificial photosynthesis: from micro-organisms to catalytic nanomaterials”, Capita Selecta Lectures of Nanoscience and Nanotechnology, K.U. Leuven (Belgium) & Erasmus Mundus partner universities, April 29 2014.
34. G. Kastrinaki, E. Daskalos, Ch. Pagkoura, N.D. Vlachos, G. Skevis, A.G. Konstandopoulos, Experimental Characterization and Numerical Simulation of Nano-Structured Conducting Membranes for Hydrogen Production from Water Splitting at Low Temperatures. 10th National Conferences on Renewable Energy Sources, 2014, Thessaloniki, Greece.
35. N. L. Kaeffer, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, M. Chavarot-Kerlidou, V. Artero, T.A. Moore, A. L. Moore and D. Gust, “Water splitting: from bio-inspiration to system integration”, Journées annuelles IMBG, May 22-23 2014, Autrans, France.
36. V. Artero, Catalytic H2 evolution : from biomimics to artificial hydrogenases and nanomaterials, Journée de Chimie de Coordination en Rhône-Alpes, April 3 2014, Grenoble, France.
37. V. Artero, Bioinspired nanocatalysts for water-splitting, Symposium on ” Nanotechnology for Sustainable Resources and Environmental Science, ACS Environmental Chemistry Division, 247th ACS National Meeting & Exposition on Chemistry &Materials for Energy, March 16-20 2014, Dallas , USA.
38. V. Artero, Cobalt-based catalysts for water splitting, Symposium on "Molecular Inorganic Chemistry at the Frontiers of Energy Research", ACS Division of Inorganic Chemistry, 247th ACS National Meeting & Exposition on Chemistry &Materials for Energy, 16-March 20 2014, Dallas , USA.
39. Romain Brisse, Nicolas Kaeffer, Serge Palacin, Vincent Artero and Bruno Jousselme. Synthesis of organic push-pull compounds for the sensitization of p-type oxides. Inverted Grätzel Solar cell. Oral Communication. 3rd International Conference on Clean and Green Energy (ICCGE 2014), 19-21 February 2014, Singapore, China.
40. V. Artero, Biomimetic, bioinspired and biosynthetic catalysts for water-splitting, International Conference for Hydrogen Production (ICH2P 2014), University of Kyushu, February 2-5 2014, Fukuoka, Japan.
41. V. Artero, Cobalt-based catalysts for electrocatalytic water splitting, invited lecture in the Department of Chemistry, Kyushu University, February 5 2014, Japan.
42. V. Artero, Biomimetic, bioinspired and biosynthetic catalysts for water-splitting, invited lecture in the Department of Chemistry, University of Nagoya, January 30 2014, Japan.
43. T. Bourgeteau, D. Tondelier, B. Geffroy, R. Brisse, C. Laberty-Robert, S. Campidelli, R. de Bettignies, V. Artero, S. Palacin, B. Jousselme, “MNPC (Matériaux et Nanostructures Pi-Conjugués), Couplage direct OPV-catalyseur : vers le stockage de l’énergie solaire sous forme chimique“, Annecy, MNPC (Matériaux et Nanostructures Pi-Conjugués), 7-11 October 2013
44. Tiphaine Bourgeteau, Bernard Geffroy, Denis Tondelier, Romain Brisse, Christel Laberty-Robert, Rémi de Bettignies, Jennifer Fize, Vincent Artero, Serge Palacin, Bruno Jousselme, Direct photosensitization of MoS3 by polymer-fullerene bulk heterojunction solar cells for hydrogen photo-production. Oral communication, Solar Energy For World Peace, 17-19 August, 2013, Istanbul, Turkey.
45. Tiphaine Bourgeteau, Bernard Geffroy, Denis Tondelier, Romain Brisse, Christel Laberty-Robert, Rémi de Bettignies, Jennifer Fize, Vincent Artero, Serge Palacin, Bruno Jousselme, Photosensibilisation directe de MoS3 par une cellule solaire organique pour la photoproduction d’hydrogène. Oral Communication, Journées d’Electrochimie 2013, 8-12 July 2013, Paris, France.
46. S. Palacin, Les systèmes catalytiques et photocatalytiques sans métaux nobles. Congrès Général de la Société Française de Physique, 1-5 July 2013, Marseille, France.
47. M. Chavarot−Kerlidou, N. Queyriaux, N. Kaeffer, J. Fize, M. Fontecave, V. Artero, Dye−sensitized nanostructured mesoporous ITO films for photoelectrochemical applications, Journée « Electrochimie Alpes », September 19 2013, Grenoble, France.
48. Kastrinaki G., Daskalos Ε., Pagkoura C., Vlachos N.D., Skevis G., Konstandopoulos A.G., Vardavoulias M., Jaén M., Saracco G. (2015) "Synthesis and Numerical Simulation of Nanostructured Transparent Conductive Oxide Membranes for Water Splitting at Low-Temperatures", in the 14th Conference of the European Ceramic Society (ECerS XIV), Toledo, Spain, June 21-25.

Commercialization of products obtained as outcomes from the R&D activities of the project:
• A nickel oxide screen printable paste has been developed during the project and transformed into a commercial product. The new ink is now sold by SOLARONIX under the commercial name Ni-nanoxide N/SP: http://shop.solaronix.com/ni-nanoxide-n-sp.html

Posters in International Workshops and Conferences:
1. “System integration: implementing molecular photo/catalytic components into an overall water-splitting tandem cell“ N. Kaeffer, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, M. Chavarot-Kerlidou, V. Artero, T.A. Moore, A. L. Moore and D. Gust; Gordon Research Seminar & Gordon Research Conference on Renewable Energy: Solar Fuels, Ventura (CA), USA, 19-24 January 2014.
2. “System integration: implementing molecular photo/catalytic components into an overall water-splitting tandem cell“ N. Kaeffer, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, M. Chavarot-Kerlidou, V. Artero, T.A. Moore, A. L. Moore and D. Gust; Journée de l’Ecole doctorale Chimie et sciences du Vivant, Grenoble, 25 april 2014.
3. “Modular synthesis by click chemistry and full characterization of new dinuclear ruthenium-copper complex“ Eugen Andreiadis, Nicolas Queyriaux, Murielle Chavarot-Kerlidou, Marc Fontecave, Vincent Artero, Brad Veldkamp, Eric Margulies, Michael Wasielewski; Journée de l’Ecole doctorale Chimie et Sciences du Vivant, Grenoble, 24 April 2014.
4. “Functionalizing ruthenium-based photosensitizers for DSPECs applications”, N. Queyriaux, V. Artero and M. Chavarot-Kerlidou, 1st International Solar Fuels Meeting, Uppsala, Sweden, April 26th – May 1st 2015.
5. “Playing with (photo)cathodes based on cobalt diimine-dioxime complexes towards their integration in device”. N. Kaeffer, A. Morozan, M. Chavarot-Kerlidou, V. Artero, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, T.A. Moore, A. L. Moore, D. Gust, April 2015, 1st International Solar Fuels Conference, Uppsala, Sweden.
6. “Playing with (photo)cathodes based on cobalt diimine-dioxime complexes towards their integration in device”, N. Kaeffer, A. Morozan, M. Chavarot-Kerlidou, V. Artero, M. Fournier, D. Méndez-Hernández, M. Tejeda, E. Reyes, J. Tomlin, T.A. Moore, A. L. Moore, D. Gust, July 2015, Congrès 2015 de la Société Chimique de France - Chimie et Transition Energétique, Lille, France.
7. “One-Dimensional Nanostructured Semiconductor Materials for Photo-electrochemical Solar Hydrogen Production“, Hernández S., Ottone C., Thalluri S.M., Chiodoni A., Russo N., Saracco G., Pirri C.F., CAMURE 2014, December 7-10, Lyon, France. http://www.camure2014.fr.
8. “A push-pull type dye associated to a new CoII HER catalyst. Toward a new hydrogen photo-production system”. R. Brisse, T. Bourgeteau, N. Kaeffer, B. Geffroy, S. Palacin, V. Artero, B. Jousselme. MNPC 2013- Annecy (France), 7 - 11 October 2013
9. “Study of activity and reaction kinetics of photocatalytic water oxidation systems using a bubbling reactor and its modeling“, Hernández S., Bensaid S., Ottone C., Armandi M., Bonelli B., Garrone E., Pirri C.F., Saracco G. Workshop – Interface between Experimental and Theoretical Approaches to Energy-Related Enzyme Catalysis, 2-4 June, 2014, London, UK.
10. Kastrinaki G., Daskalos E., Pagkoura C., Vlachos N.D., Skevis G., Konstandopoulos A.G., Vardavoulias M., Jaén M., Hernandez S., Saracco G. (2015) "Numerical Simulation for the Design and Performance of Nanostructured Transparent Conducting Oxide Membranes for Hydrogen Production from Water Splitting at Low-Temperatures", in the European Aerosol Conference (EAC 2015), Milan, Italy, September 6-11, 2015.
11. “A red to blue series of new organic dyes for photocathodes” R. Brisse, T. Bourgeteau, B. Geffroy and B. Jousselme. April 2015, 1st International Solar Fuels Conference, Uppsala, Sweden.
12. "Direct photosensitization of MoS3 by polymer-fullerene bulk heterojunction solar cells for hydrogen photoproduction", T. Bourgeteau, R. Brisse, D. Tondelier, B. Geffroy, C. Laberty-Robert, R. de Bettignies, J. Fize, V. Artero, S. Palacin, B. Jousselme. Conférence ElecMol 2012, December 2012, Grenoble, France. Awarded with a poster prize.
13. "Toward the construction of fully molecular photocathodes for hydrogen evolution", N. Kaeffer, R. Brisse, J. Massin, A. Morozan, C. Windle, B. Jousselme, M. Chavarot-Kerlidou, V. Artero, Gordon Research Conference on Renewable Energy: Solar Fuels 27-28 February 2016, Borgo, Italy.
14. «Photocathodes based on organic semiconductors coupled to a MoS3 catalyst for solar hydrogen production », T. Bourgeteau, D. Tondelier, B. Geffroy, V. Artero, B. Jousselme. International Solar Fuel conference (ISF-1), April 2015, Uppsala, Sweden. Selected for flash talk (3 min) session during the conference.

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www.artiphyction.org

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Record Number: 188122 / Last updated on: 2016-08-11