Periodic Reporting for period 2 - eSCALED (European School on Artificial Leaf : Electrodes Devices)
Periodo di rendicontazione: 2020-04-01 al 2022-09-30
Climate change resulting from accumulation of anthropogenic carbon dioxide in the atmosphere and the uncertainty in the amount of recoverable fossil fuel reserves are driving forces for the development of renewable, carbon-neutral energy technologies. Artificial photosynthesis appears to be an appealing approach for a sustainable energy generation as it produces “solar fuels” or commodities for chemistry in a stable and storable chemical form, from solar energy, H2O & CO2.
The eSCALED project is a contribution to structure early-stage research training at the European level and strengthen European innovation capacity to elaborate an artificial leaf. The ESR will be in charge of combining in a unique device a solar cell and a bioinspired electrochemical stack where H2O oxidation and H+ or CO2 reduction are performed in microreactors.
The novelties in this project are at two levels: (1) Developing sustainable joint doctoral degree structure based on inter/multidisciplinary aspects of biological/biochemical, condensed, inorganic & soft matter to device engineering and innovation development. (2) Scientifically using, cheap and easy processes tandem organic solar cells, earth-abundant materials for water splitting, new generation of catalysts and natural/artificial hydrogenase enzymes for hydrogen production, formate dehydrogenases for catalytic carbon dioxide reduction, new proton-exchange fluorinated membranes and finally, electrode micro porosity to mimic the chloroplasts of a plant. The eSCALED collaborative project brings together for the first time, 11 internationally recognized academic and industrial research groups. The project has an interdisciplinary scientific approach integrating the latest knowledge on catalysis, photovoltaic and polymer chemistry for self-structuration. Major outcomes will include breakthroughs in the development of artificial photosynthetic leaf as a photoelectrochemical device, highly trained researchers & new partners collaborations.
The eSCALED project is a contribution to structure early-stage research training at the European level and strengthen European innovation capacity to elaborate an artificial leaf. The ESR will be in charge of combining in a unique device a solar cell and a bioinspired electrochemical stack where H2O oxidation and H+ or CO2 reduction are performed in microreactors.
The novelties in this project are at two levels: (1) Developing sustainable joint doctoral degree structure based on inter/multidisciplinary aspects of biological/biochemical, condensed, inorganic & soft matter to device engineering and innovation development. (2) Scientifically using, cheap and easy processes tandem organic solar cells, earth-abundant materials for water splitting, new generation of catalysts and natural/artificial hydrogenase enzymes for hydrogen production, formate dehydrogenases for catalytic carbon dioxide reduction, new proton-exchange fluorinated membranes and finally, electrode micro porosity to mimic the chloroplasts of a plant. The eSCALED collaborative project brings together for the first time, 11 internationally recognized academic and industrial research groups. The project has an interdisciplinary scientific approach integrating the latest knowledge on catalysis, photovoltaic and polymer chemistry for self-structuration. Major outcomes will include breakthroughs in the development of artificial photosynthetic leaf as a photoelectrochemical device, highly trained researchers & new partners collaborations.
The scientific progress of the project has advanced as expected
Water Oxidation catalysts: a number of synthetic strategies have been developed for the preparation of MOFs based on Ru-tda water oxidation catalyst complexes and Ru-carbanionic complexes, properly functionalized with axial pyridyl ligands containing carboxylic groups and ZrOx. In addition, a thorough spectroscopic characterization of reactive intermediates related to the WO catalyst based on Cu and tetra-amidate ligands has been carried out using fast transient absorption spectroscopy methods.
Reductive Catalysis: Catalysts for Hydrogen evolution have included a cobalt macrocycles and diiron mimics of FeFe hydrogenases active sites and CO2-reducing catalysts are organometallic Rhenium and rhodium complexes as well as Ni(cyclam) complexes. Semi-artificial hydrogenases have been developed and characterized, as an O2-tolerant natural hydrogenase. All catalysts have been interfaced with electrode materials (carbon nanotubes via pyrene groups enabling π-π interaction with CNT sidewalls or hierarchical porous carbon) and their catalytic activity and stability has been evaluated under aqueous or non-aqueous conditions.
Synthesis of novel materials:
*light harvesting material, synthesis of perovskites nanocrystals (NCs) has been developed following two different methods to make solution processable CsPbBr3 nanocrystals, obtaining good quality CsPbBr3 nanocrystals able to disperse in common organic solvents.
*electrode: materials have been developed thinking of three different strategies, depending on the position of the electrodes relative to the membrane. Different polymers have been synthetized for every strategy, and modified in order to include reactive groups that can anchor the catalysts.
*membranes: 4 copolymers and 1 new polymer modification have been achieved. Homo and copolymers (statistical/ block copolymers) have been synthesized achieving large batch quantities (500g).
Deposition of systems: different solar cells have been done including single junction solar cells based on p-i-n photovoltaic cells (solution processed CsPbBr3 NCs), p-i-n wide-bandgap perovskite solar cells, p-i-n narrow-bandgap perovskite solar cells, tandem perovskite-perovskite cells (1) and perovskite-silicon cells (2). For the membranes, PEM & ionomers have been deposited up to 30x30 cm (proton conductivities up to 300 mS/cm). Membrane-electrode assemblies (MEAs) with the catalyst have been developed.
A fully printed device integrating the MEAs (solar to hydrogen (STH) conversion 14%) and a continuous flow light-driven water splitting system with tandem cells (STH 18,6% (1) and 21,5% (2)) have been developed.
LCA and LCC assessments has been finalized. Hence, the environmental and economic profiling for the different parts of the device have been performed. In all cases, studies have brought recommendations and potential improvements with the view of transfer results to higher TRLs and even in some cases, providing alternatives once technologies reach the market.
15 publications accepted, 1 submitted and 14 being prepared for submission. 2 patent applications filled. A 3rd patent is being prepared.
39 abstracts accepted (18 presentations and 21 posters). In addition, the 14 ESRs participated in the Summer School.
Water Oxidation catalysts: a number of synthetic strategies have been developed for the preparation of MOFs based on Ru-tda water oxidation catalyst complexes and Ru-carbanionic complexes, properly functionalized with axial pyridyl ligands containing carboxylic groups and ZrOx. In addition, a thorough spectroscopic characterization of reactive intermediates related to the WO catalyst based on Cu and tetra-amidate ligands has been carried out using fast transient absorption spectroscopy methods.
Reductive Catalysis: Catalysts for Hydrogen evolution have included a cobalt macrocycles and diiron mimics of FeFe hydrogenases active sites and CO2-reducing catalysts are organometallic Rhenium and rhodium complexes as well as Ni(cyclam) complexes. Semi-artificial hydrogenases have been developed and characterized, as an O2-tolerant natural hydrogenase. All catalysts have been interfaced with electrode materials (carbon nanotubes via pyrene groups enabling π-π interaction with CNT sidewalls or hierarchical porous carbon) and their catalytic activity and stability has been evaluated under aqueous or non-aqueous conditions.
Synthesis of novel materials:
*light harvesting material, synthesis of perovskites nanocrystals (NCs) has been developed following two different methods to make solution processable CsPbBr3 nanocrystals, obtaining good quality CsPbBr3 nanocrystals able to disperse in common organic solvents.
*electrode: materials have been developed thinking of three different strategies, depending on the position of the electrodes relative to the membrane. Different polymers have been synthetized for every strategy, and modified in order to include reactive groups that can anchor the catalysts.
*membranes: 4 copolymers and 1 new polymer modification have been achieved. Homo and copolymers (statistical/ block copolymers) have been synthesized achieving large batch quantities (500g).
Deposition of systems: different solar cells have been done including single junction solar cells based on p-i-n photovoltaic cells (solution processed CsPbBr3 NCs), p-i-n wide-bandgap perovskite solar cells, p-i-n narrow-bandgap perovskite solar cells, tandem perovskite-perovskite cells (1) and perovskite-silicon cells (2). For the membranes, PEM & ionomers have been deposited up to 30x30 cm (proton conductivities up to 300 mS/cm). Membrane-electrode assemblies (MEAs) with the catalyst have been developed.
A fully printed device integrating the MEAs (solar to hydrogen (STH) conversion 14%) and a continuous flow light-driven water splitting system with tandem cells (STH 18,6% (1) and 21,5% (2)) have been developed.
LCA and LCC assessments has been finalized. Hence, the environmental and economic profiling for the different parts of the device have been performed. In all cases, studies have brought recommendations and potential improvements with the view of transfer results to higher TRLs and even in some cases, providing alternatives once technologies reach the market.
15 publications accepted, 1 submitted and 14 being prepared for submission. 2 patent applications filled. A 3rd patent is being prepared.
39 abstracts accepted (18 presentations and 21 posters). In addition, the 14 ESRs participated in the Summer School.
To answer the general objectives the eSCALED project is envisioned as 4 years project in which each partner will use their skills and knowledge to get to the following specific objectives:
• Synthesis and characterization (chemical, structural and electrochemical) of ordered mesoporous electrodes that must: 1) be easily processable and up scalable 2) present a high stability under oxidative conditions 3) reach a high proton conductivity and 4) present surface functional groups able to bind the catalyst
• Synthesis and characterization of efficient heterogeneous catalysts as nanoparticles
• Synthesis and characterization of efficient homogeneous catalysts with improved stability under turnover and intrinsic activity in terms of overpotential requirement and turnover frequency under technologically relevant conditions. Functionalization of these catalysts with groups that allow anchoring them on electrode surfaces.
• Processing of the catalyst onto the electrodes. Characterization and optimization of electro-catalytic properties
• Development of organic and perovskite solar cells to drive reduction/oxidation reactions using the catalytic electrodes. The solar cells will be designed specifically to have its maximum power point at the voltage that is defined by the standard and overpotentials of the catalysts and the surface area. For this purpose new tailored semiconductor materials will be developed.
• Proof-of-concept. Water splitting under applied bias using the catalytic electrodes.
• Fabrication of integrated light driven and self-sustained water oxidation/CO2 reduction devices using materials and conversion concepts from eSCALED. Determine efficiency and stability.
• Life cycle analysis of catalysts, electrodes and membranes upscaled production leading to their final assembly.
Moreover, to better face the challenges of the Renewable Energies field, eSCALED training network will give the ESRs a multi/transdisciplinary cross-national preparation broadening their frontiers for the working environment.
• Synthesis and characterization (chemical, structural and electrochemical) of ordered mesoporous electrodes that must: 1) be easily processable and up scalable 2) present a high stability under oxidative conditions 3) reach a high proton conductivity and 4) present surface functional groups able to bind the catalyst
• Synthesis and characterization of efficient heterogeneous catalysts as nanoparticles
• Synthesis and characterization of efficient homogeneous catalysts with improved stability under turnover and intrinsic activity in terms of overpotential requirement and turnover frequency under technologically relevant conditions. Functionalization of these catalysts with groups that allow anchoring them on electrode surfaces.
• Processing of the catalyst onto the electrodes. Characterization and optimization of electro-catalytic properties
• Development of organic and perovskite solar cells to drive reduction/oxidation reactions using the catalytic electrodes. The solar cells will be designed specifically to have its maximum power point at the voltage that is defined by the standard and overpotentials of the catalysts and the surface area. For this purpose new tailored semiconductor materials will be developed.
• Proof-of-concept. Water splitting under applied bias using the catalytic electrodes.
• Fabrication of integrated light driven and self-sustained water oxidation/CO2 reduction devices using materials and conversion concepts from eSCALED. Determine efficiency and stability.
• Life cycle analysis of catalysts, electrodes and membranes upscaled production leading to their final assembly.
Moreover, to better face the challenges of the Renewable Energies field, eSCALED training network will give the ESRs a multi/transdisciplinary cross-national preparation broadening their frontiers for the working environment.