Periodic Reporting for period 2 - ELCOREL (Electrochemical Conversion of Renewable Electricity into Fuels and Chemicals)
Okres sprawozdawczy: 2019-05-01 do 2021-04-30
The efficient and environmentally sustainable generation of energy is the most pressing challenge for European science and technology in the 21st century. The increasing environmental awareness of European societies, together with depletion of easily accessible fossil fuels and geostrategic considerations, calls for a paradigm shift away from large-scale technologies that deploy limited reserves and generate huge amounts of waste. Renewable energy sources, such as biomass and solar or wind energy, are the only viable long-term alternative for an infrastructure based on the concepts of recycling and the distributed generation, storage and use of energy.
The large-scale implementation of renewable energy sources necessitates the introduction of technology that can deal with the intermittent nature of renewable energy sources and their restricted predictability. These technical problems can be successfully mitigated through electrochemical technologies. While electricity is traditionally stored in electrochemical devices such as supercapacitors and batteries, large-scale implementation of renewable electricity will require to extend the existing energy storage technologies by the (photo-)electrochemical conversion to fuels and other chemicals, such as hydrogen obtained from water splitting, or small organic molecules obtained through electrochemical carbon dioxide reduction.
The scientific objectives of ELCOREL are: (1) to deploy a systematic theoretical description of electrocatalysis by means of quantum chemical calculations to gain fundamental insight into the rational design of electrocatalysts for water oxidation and CO2 reduction; (2) to implement advanced techniques of material synthesis to prepare novel nano-particulate catalysts for multiple electron redox reactions meeting the predictions of the rational computational design; (3) to investigate the dynamics of nanostructured metal and metal-oxide interfaces in the electrocatalytic processes using state-of-the-art electrochemical and spectroscopic techniques and (4) to engineer the knowledge and materials developed under (1)-(3) into working electrochemical applications which meet the cost and scale requirements of the industrial partners, and (5) to transfer the knowledge to the public so that the society can discuss the best options for the implementation of the Paris agreement to reshape the society based on carbon energy into the one based on renewable energy sources.
The large-scale implementation of renewable energy sources necessitates the introduction of technology that can deal with the intermittent nature of renewable energy sources and their restricted predictability. These technical problems can be successfully mitigated through electrochemical technologies. While electricity is traditionally stored in electrochemical devices such as supercapacitors and batteries, large-scale implementation of renewable electricity will require to extend the existing energy storage technologies by the (photo-)electrochemical conversion to fuels and other chemicals, such as hydrogen obtained from water splitting, or small organic molecules obtained through electrochemical carbon dioxide reduction.
The scientific objectives of ELCOREL are: (1) to deploy a systematic theoretical description of electrocatalysis by means of quantum chemical calculations to gain fundamental insight into the rational design of electrocatalysts for water oxidation and CO2 reduction; (2) to implement advanced techniques of material synthesis to prepare novel nano-particulate catalysts for multiple electron redox reactions meeting the predictions of the rational computational design; (3) to investigate the dynamics of nanostructured metal and metal-oxide interfaces in the electrocatalytic processes using state-of-the-art electrochemical and spectroscopic techniques and (4) to engineer the knowledge and materials developed under (1)-(3) into working electrochemical applications which meet the cost and scale requirements of the industrial partners, and (5) to transfer the knowledge to the public so that the society can discuss the best options for the implementation of the Paris agreement to reshape the society based on carbon energy into the one based on renewable energy sources.
The activity concentrated on systematic investigations of the nature of electrocatalytic oxygen evolution and carbon dioxide reduction, development of novel catalysts and their implementation into test electrolyzers.
In respect to electrocatalytic oxygen evolution the consortium extended the DFT based computational techniques to develop fundamentally error model of the oxygen evolution thermodynamics on semiconducting oxides. This model outlines and removes the intrinsic drawback of the conventional model(s) which are unable to replicate correctly the binding energy of the oxo intermediates on semiconducting surfaces. This model was further extebded introducing a co-doping concept when a semiconductor is simultaneously n and p doped to improve its electric and catalytic activity. This concept was conceived for Ti oxides to avoid the use of Ru and Ir in acid media water electrolysis and was experimentally validated. The consortium also developed low temperature synthesis of nanoparticulate catalysts both for acid as well as alkaline media, namely pyrochlore based catalyst based utilizing synregy Ru and Ir with reduced transition metal content to increase activity and improved stability. Novel Ni based catalysts were developed by exfoliation of nanoparticulate LaNiO3 and by engineering of the Ni based coatings for alkaline water electrolysis.
In respect to catalytic carbon dioxide reaction the consortium followed the two directions leading to controlled 2 electron reduction (to CO or formic acid) as well as multiple electron reduction to alcohols and hydrocarbons. In the case of the 2 electron reduction we have employed quantum chemical methods to describe the role of single atom catalysts both on carbon as well as on copper and copper chalcogenide based surfaces. From the experimental point of view the consortium performed systematic investigations of the local pH and present cationic species on the CO2 reduction process. In the case of the multiple electron reduction of carbon dioxide the main attention was paid to Co porphyrine modified carbon multi-wall nanotubes. The selectivity of the process is achieved by a variation of temperature when the formation of gaseous products (mainly of the methane) is promoted at increased temperatures. The industrial consortium members also developed procedures for integration of nanocrystalline alloy catalyst into gas diffusion electrodes and their integration into electrolyzer.
In respect to electrocatalytic oxygen evolution the consortium extended the DFT based computational techniques to develop fundamentally error model of the oxygen evolution thermodynamics on semiconducting oxides. This model outlines and removes the intrinsic drawback of the conventional model(s) which are unable to replicate correctly the binding energy of the oxo intermediates on semiconducting surfaces. This model was further extebded introducing a co-doping concept when a semiconductor is simultaneously n and p doped to improve its electric and catalytic activity. This concept was conceived for Ti oxides to avoid the use of Ru and Ir in acid media water electrolysis and was experimentally validated. The consortium also developed low temperature synthesis of nanoparticulate catalysts both for acid as well as alkaline media, namely pyrochlore based catalyst based utilizing synregy Ru and Ir with reduced transition metal content to increase activity and improved stability. Novel Ni based catalysts were developed by exfoliation of nanoparticulate LaNiO3 and by engineering of the Ni based coatings for alkaline water electrolysis.
In respect to catalytic carbon dioxide reaction the consortium followed the two directions leading to controlled 2 electron reduction (to CO or formic acid) as well as multiple electron reduction to alcohols and hydrocarbons. In the case of the 2 electron reduction we have employed quantum chemical methods to describe the role of single atom catalysts both on carbon as well as on copper and copper chalcogenide based surfaces. From the experimental point of view the consortium performed systematic investigations of the local pH and present cationic species on the CO2 reduction process. In the case of the multiple electron reduction of carbon dioxide the main attention was paid to Co porphyrine modified carbon multi-wall nanotubes. The selectivity of the process is achieved by a variation of temperature when the formation of gaseous products (mainly of the methane) is promoted at increased temperatures. The industrial consortium members also developed procedures for integration of nanocrystalline alloy catalyst into gas diffusion electrodes and their integration into electrolyzer.
The main progress beyond the state of the art is found in the following areas:
i) in the activities relevant to the oxygen evolving catalysts a completely novel theoretical concept was outline which opens a way for a final replacement of Ru and Ir oxides from practical water electrolysis on acid media.The novel theoretical approaches were also utilized in prediction of the behavior of reconstructued oxide surface. The theoretical models were mirrored in synthesis of novel nanoparticulate catalysts based on Ni based perovskites where the local structure allowed to exfoliate of highly active sites to the catalyst surface.
ii) in the activities relevant to carbon dioxide reduction the main progress beyond the state of the art was achieved in theoretical description of the the single transition metal atom catalysts and their selectivity control. From the experimental point of view the main progress is seen in elucidation of the supporting electrolyte role in steering the selectivity of the CO2 reduction towards CO or formic acid. The work focusing on higher utilization of the carbon dioxide towards alcohols utilized mainly the Co porphyrine modified multiwal carbon nanotubes as versatile catalysts. The formate producing catalysts were integrated into gas diffusion electrodes to prove the feasibility of electrolytic formate production on large scale production.
i) in the activities relevant to the oxygen evolving catalysts a completely novel theoretical concept was outline which opens a way for a final replacement of Ru and Ir oxides from practical water electrolysis on acid media.The novel theoretical approaches were also utilized in prediction of the behavior of reconstructued oxide surface. The theoretical models were mirrored in synthesis of novel nanoparticulate catalysts based on Ni based perovskites where the local structure allowed to exfoliate of highly active sites to the catalyst surface.
ii) in the activities relevant to carbon dioxide reduction the main progress beyond the state of the art was achieved in theoretical description of the the single transition metal atom catalysts and their selectivity control. From the experimental point of view the main progress is seen in elucidation of the supporting electrolyte role in steering the selectivity of the CO2 reduction towards CO or formic acid. The work focusing on higher utilization of the carbon dioxide towards alcohols utilized mainly the Co porphyrine modified multiwal carbon nanotubes as versatile catalysts. The formate producing catalysts were integrated into gas diffusion electrodes to prove the feasibility of electrolytic formate production on large scale production.