Electrochemical conversion of nitrogen to ammonia-experimental and theoretical studies- Early Energy Catalysts Calls (2)
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
This project is concerned with exciting developments of new electro-catalytic technologies for Green eNH3 production with the energy derived from wind power. This contrasts with the traditional catalytic process for industrial NH3 production
where non-renewable natural gas is used as the energy and H2 source with a concomitant release of large CO2 emission. Thus, the development of new renewable electrocatalytic technologies can substantially reduce carbon emission by
utilizing wind energy to produce carbon free NH3. This electrification of the chemical industry will improve energy security by reducing the dependency on dwindling supply of natural gas. Further applications of eNH3 for energy storage and transportation will reduce the cost of integrating renewable into the energy mix. Oxford University and STFC will collaborate with Siemens, UK to explore various new catalytic surfaces to produce ammonia from nitrogen and hydrogen (or water) by electrochemical means. This program is part of a wider consortium which is making the UK a central research hub for Green Ammonia. Three different workstreams will be carried out as follows:
Workstream 1. Management and Commercial Analysis (Lead partner Siemens). This portion of the project is focused on the management of the project and assessment of the commercial feasibility of the technology. Results from the 2 technical workstreams will be used to develop commercial models of the potential end systems.
Workstream 2. Experimental analysis (Lead Partner Oxford University). This work is divided into 3 work packages each focusing on a different Nafion based system. Key figures of merit will be established i.e. NH3 reaction rate, faradaic efficiency, time stability, voltage characteristics.
Workstream 3. Theoretical Analysis (Lead Partner Siemens). In conjunction with sub-contractors (OCF plc) and academic partner at STFC. This work stream is divided into 4 work packages. All results will be regularly exchanged with the other workstreams and will share 3 top level milestones. The work stream will be divided into 2 phases aligned with the work being undertaken in workstreams 1 and 2.
where non-renewable natural gas is used as the energy and H2 source with a concomitant release of large CO2 emission. Thus, the development of new renewable electrocatalytic technologies can substantially reduce carbon emission by
utilizing wind energy to produce carbon free NH3. This electrification of the chemical industry will improve energy security by reducing the dependency on dwindling supply of natural gas. Further applications of eNH3 for energy storage and transportation will reduce the cost of integrating renewable into the energy mix. Oxford University and STFC will collaborate with Siemens, UK to explore various new catalytic surfaces to produce ammonia from nitrogen and hydrogen (or water) by electrochemical means. This program is part of a wider consortium which is making the UK a central research hub for Green Ammonia. Three different workstreams will be carried out as follows:
Workstream 1. Management and Commercial Analysis (Lead partner Siemens). This portion of the project is focused on the management of the project and assessment of the commercial feasibility of the technology. Results from the 2 technical workstreams will be used to develop commercial models of the potential end systems.
Workstream 2. Experimental analysis (Lead Partner Oxford University). This work is divided into 3 work packages each focusing on a different Nafion based system. Key figures of merit will be established i.e. NH3 reaction rate, faradaic efficiency, time stability, voltage characteristics.
Workstream 3. Theoretical Analysis (Lead Partner Siemens). In conjunction with sub-contractors (OCF plc) and academic partner at STFC. This work stream is divided into 4 work packages. All results will be regularly exchanged with the other workstreams and will share 3 top level milestones. The work stream will be divided into 2 phases aligned with the work being undertaken in workstreams 1 and 2.
Planned Impact
Ammonia is a commodity and the sole differentiators from the customers/market perspective are price and environmental impact. The business opportunity is to deliver a carbon-free production process for ammonia which can then be utilized as
a flexible asset for 4 sub-areas:
(i) Currently ammonia is used as a feedstock for the chemical industry. About 80% is used in the fertilizer industry with the
remaining 20% being used in varied range o chemical pro-cesses and the plastics industry.
(ii) As an energy storage medium for heat and electricity, which can be turned into heat/electricity (via gas turbines or fuel cells) on demand. (short-medium opportunity)
(iii) A fuel for the transportation sector.
(iv) As a highly efficient hydrogen carrier, thereby supporting the implementation of the Hydrogen Economy. There is currently no cost-competitive renewable based carbon-free synthetic route in the marketplace. If this technical feasibility study is successful, the impact for this new electrochemical synthesis method is (a) Carbon-free, (b) capable of integration with an intermittent energy source and (c) achieves high efficiencies. Thus, the key technology in such a synthesis and output from this work, will be the Membrane Electrode Assembly (MEA), which could be integrated with a source of intermittent electricity generation.
a flexible asset for 4 sub-areas:
(i) Currently ammonia is used as a feedstock for the chemical industry. About 80% is used in the fertilizer industry with the
remaining 20% being used in varied range o chemical pro-cesses and the plastics industry.
(ii) As an energy storage medium for heat and electricity, which can be turned into heat/electricity (via gas turbines or fuel cells) on demand. (short-medium opportunity)
(iii) A fuel for the transportation sector.
(iv) As a highly efficient hydrogen carrier, thereby supporting the implementation of the Hydrogen Economy. There is currently no cost-competitive renewable based carbon-free synthetic route in the marketplace. If this technical feasibility study is successful, the impact for this new electrochemical synthesis method is (a) Carbon-free, (b) capable of integration with an intermittent energy source and (c) achieves high efficiencies. Thus, the key technology in such a synthesis and output from this work, will be the Membrane Electrode Assembly (MEA), which could be integrated with a source of intermittent electricity generation.
People |
ORCID iD |
| SCE Tsang (Principal Investigator) |
Publications
Ayvali T
(2021)
The Position of Ammonia in Decarbonising Maritime Industry: An Overview and Perspectives: Part II : Costs, safety and environmental performance and the future prospects for ammonia in shipping
in Johnson Matthey Technology Review
Ayvali T
(2021)
The Position of Ammonia in Decarbonising Maritime Industry: An Overview and Perspectives: Part I : Technological advantages and the momentum towards ammonia-propelled shipping
in Johnson Matthey Technology Review
Fellowes J
(2018)
Electrochemical Ammonia Synthesis in Barium-Cerium Zirconate Cells
in ECS Meeting Abstracts
Lau THM
(2018)
Transition metal atom doping of the basal plane of MoS2 monolayer nanosheets for electrochemical hydrogen evolution.
in Chemical science
McPherson I
(2019)
The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl-KCl Eutectics
in Angewandte Chemie
McPherson I
(2018)
Electrochemical Ammonia Synthesis in Molten Salts
in ECS Meeting Abstracts
McPherson IJ
(2019)
The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl-KCl Eutectics.
in Angewandte Chemie (International ed. in English)
McPherson IJ
(2019)
Materials for electrochemical ammonia synthesis.
in Dalton transactions (Cambridge, England : 2003)
Mo J
(2020)
Transition metal atom-doped monolayer MoS2 in a proton-exchange membrane electrolyzer
in Materials Today Advances
Mo J
(2019)
Superior Performance of Ag over Pt for Hydrogen Evolution Reaction in Water Electrolysis under High Overpotentials
in ACS Applied Energy Materials
| Description | The research of this award has been completed. Although we have found a promising electrode material for the electrochemical production of ammonia at low temperature the yield and rate was unfortunately too low for commercial exploitation. On the other hand, H2 production from electrochemical reduction over some catalyst materials has appeared to be more promising. |
| Exploitation Route | Further work following this award is in progress. Electrochemical H2 production over Ag based materials under higher over-potential has appeared to be a promising direction. The Ag based catalysts were found to be cheaper than the standard 20% Pt/C as cathode. The finding was provisionally patented on the behalf of Oxford University. Discussion with Siemens is underway. |
| Sectors | Chemicals,Energy,Environment,Transport |
| Description | A patent based on this award was filed on behalf of Oxford University. The potential impacts of this research are the energy, environment and chemical production. Discussions with industrial partners are ongoing. |
| Sector | Chemicals,Creative Economy,Energy,Environment |
| Impact Types | Societal,Economic |
| Title | developed electrochemical cells and analytical method for electrochemical production of ammonia through modified nafion membrane |
| Description | the construction of a dedicated bench - scale electrochemical setup with H2/NH3 analysis, current density evaluation as well as impedance measurement |
| Type Of Material | Improvements to research infrastructure |
| Year Produced | 2018 |
| Provided To Others? | No |
| Impact | We are in the process of writing up the development of this cells and methodology for publication in a peer review journal |
| Description | Collaboration with Siemens, AG. |
| Organisation | Siemens AG |
| Country | Germany |
| Sector | Private |
| PI Contribution | This research was funded by IUK with the contribution from Siemens, plc. We have demonstrated the research ability and focus of the team to them. From there we have some following up research grants with Siemens plc and Siemens AG. For example, there is a seed fund recently obtained to work with Siemens, AG (about 15K) on the electrochemical conversion of CO2 to hydrocarbons. |
| Collaborator Contribution | Siemens continues to work with us by regularly exchange ideas and ask our involvement in the potential EU applications of Horizon 2020. |
| Impact | At this stage, some joint research papers and provisional patents have been produced. |
| Start Year | 2016 |
| Description | Electrochemical conversion of nitrogen to ammonia: experimental and theoretical studies |
| Organisation | Science and Technologies Facilities Council (STFC) |
| Department | High Performance Computing (HPC) |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | In this project, catalytic production of ammonia and hydrogen by electrochemical means was studied both experimentally and theoretically through the collaboration with Siemens, AG, Siemens,plc in Harwell and STFC-computing in Daresbury. At Oxford, our main contribution included the construction of a dedicated bench - scale electrochemical setup for ammonia and hydrogen production, which was designed and built at the University of Oxford during the setting up phase of the project (April - July '16). We also synthesized literature reported and new potential electro-catalysts, tested and evaluated their productivity. |
| Collaborator Contribution | For Siemens,plc and Siemens AG. Their project comprised the work packages. Management of the overall project (this work package) was performed by the Lead Project Manager - provided by Siemens - with a remit to ensure the appropriate synchronisation of, and facilitate relationships between, the separate work packages. The deliverables of this work package were made timely (commercial) and evaluations of the electrochemical cell configurations were investigated. Their lead project manager was also responsible for: - Co-ordinating quarterly project review meetings - Risk and issue management, including maintenance of the project risk register. For STFC Computing unit: Establishment of an efficient and re-usable modeling methodology work flow. Providing detailed information on the Sm2-xSrxNiO4 and SmFe0.7Cu0.3-xNixO3 systems with different amounts of substitution, e.g. bulk structure, surface properties and potential reactive centres. Comparing the active reaction centres and the origin of the improved material performance, which guided the improvement of electrode materials. Extension of the experience gained from the ceramic systems to apply it to an alloy based system. |
| Impact | This consortium was multidisciplinary, which involved Siemens (AG and plc) as the industrial partner. They managed and liaised contributions from each partner to address the possible electrochemical production of ammonia and hydrogen over some reported active electrochemical materials. From Oxford, the outcomes included the construction of the desktop automatic electrochemical device which allowed to evaluate the performance of electrochemical productivity of ammonia or hydrogen over some selected catalytic materials as cathodes; although it was proved feasibility to form ammonia from N2 and H2O by this electrochemical device over these reported catalytic materials. Both the quantity and rate for ammonia production were very small than those promising values claimed in the literature. The computation approach by STFC also confirmed that these materials were unable to electrochemically reduce N2 to NH3 at a substantial way due to the competitive route of H+ reduction to H2 in water. However, some materials were found to be excellent for electrochemical production of H2 from water. As a result, two research papers in good level peer reviewed journals were published based on our findings. Recommendation to the Siemens about the electrochemical synthesis of ammonia compared to H2 in the presence of N2/water was therefore made. |
| Start Year | 2016 |
| Description | Electrochemical conversion of nitrogen to ammonia: experimental and theoretical studies |
| Organisation | Siemens AG |
| Country | Germany |
| Sector | Private |
| PI Contribution | In this project, catalytic production of ammonia and hydrogen by electrochemical means was studied both experimentally and theoretically through the collaboration with Siemens, AG, Siemens,plc in Harwell and STFC-computing in Daresbury. At Oxford, our main contribution included the construction of a dedicated bench - scale electrochemical setup for ammonia and hydrogen production, which was designed and built at the University of Oxford during the setting up phase of the project (April - July '16). We also synthesized literature reported and new potential electro-catalysts, tested and evaluated their productivity. |
| Collaborator Contribution | For Siemens,plc and Siemens AG. Their project comprised the work packages. Management of the overall project (this work package) was performed by the Lead Project Manager - provided by Siemens - with a remit to ensure the appropriate synchronisation of, and facilitate relationships between, the separate work packages. The deliverables of this work package were made timely (commercial) and evaluations of the electrochemical cell configurations were investigated. Their lead project manager was also responsible for: - Co-ordinating quarterly project review meetings - Risk and issue management, including maintenance of the project risk register. For STFC Computing unit: Establishment of an efficient and re-usable modeling methodology work flow. Providing detailed information on the Sm2-xSrxNiO4 and SmFe0.7Cu0.3-xNixO3 systems with different amounts of substitution, e.g. bulk structure, surface properties and potential reactive centres. Comparing the active reaction centres and the origin of the improved material performance, which guided the improvement of electrode materials. Extension of the experience gained from the ceramic systems to apply it to an alloy based system. |
| Impact | This consortium was multidisciplinary, which involved Siemens (AG and plc) as the industrial partner. They managed and liaised contributions from each partner to address the possible electrochemical production of ammonia and hydrogen over some reported active electrochemical materials. From Oxford, the outcomes included the construction of the desktop automatic electrochemical device which allowed to evaluate the performance of electrochemical productivity of ammonia or hydrogen over some selected catalytic materials as cathodes; although it was proved feasibility to form ammonia from N2 and H2O by this electrochemical device over these reported catalytic materials. Both the quantity and rate for ammonia production were very small than those promising values claimed in the literature. The computation approach by STFC also confirmed that these materials were unable to electrochemically reduce N2 to NH3 at a substantial way due to the competitive route of H+ reduction to H2 in water. However, some materials were found to be excellent for electrochemical production of H2 from water. As a result, two research papers in good level peer reviewed journals were published based on our findings. Recommendation to the Siemens about the electrochemical synthesis of ammonia compared to H2 in the presence of N2/water was therefore made. |
| Start Year | 2016 |
| Description | Electrochemical conversion of nitrogen to ammonia: experimental and theoretical studies |
| Organisation | Siemens AG |
| Country | Germany |
| Sector | Private |
| PI Contribution | In this project, catalytic production of ammonia and hydrogen by electrochemical means was studied both experimentally and theoretically through the collaboration with Siemens, AG, Siemens,plc in Harwell and STFC-computing in Daresbury. At Oxford, our main contribution included the construction of a dedicated bench - scale electrochemical setup for ammonia and hydrogen production, which was designed and built at the University of Oxford during the setting up phase of the project (April - July '16). We also synthesized literature reported and new potential electro-catalysts, tested and evaluated their productivity. |
| Collaborator Contribution | For Siemens,plc and Siemens AG. Their project comprised the work packages. Management of the overall project (this work package) was performed by the Lead Project Manager - provided by Siemens - with a remit to ensure the appropriate synchronisation of, and facilitate relationships between, the separate work packages. The deliverables of this work package were made timely (commercial) and evaluations of the electrochemical cell configurations were investigated. Their lead project manager was also responsible for: - Co-ordinating quarterly project review meetings - Risk and issue management, including maintenance of the project risk register. For STFC Computing unit: Establishment of an efficient and re-usable modeling methodology work flow. Providing detailed information on the Sm2-xSrxNiO4 and SmFe0.7Cu0.3-xNixO3 systems with different amounts of substitution, e.g. bulk structure, surface properties and potential reactive centres. Comparing the active reaction centres and the origin of the improved material performance, which guided the improvement of electrode materials. Extension of the experience gained from the ceramic systems to apply it to an alloy based system. |
| Impact | This consortium was multidisciplinary, which involved Siemens (AG and plc) as the industrial partner. They managed and liaised contributions from each partner to address the possible electrochemical production of ammonia and hydrogen over some reported active electrochemical materials. From Oxford, the outcomes included the construction of the desktop automatic electrochemical device which allowed to evaluate the performance of electrochemical productivity of ammonia or hydrogen over some selected catalytic materials as cathodes; although it was proved feasibility to form ammonia from N2 and H2O by this electrochemical device over these reported catalytic materials. Both the quantity and rate for ammonia production were very small than those promising values claimed in the literature. The computation approach by STFC also confirmed that these materials were unable to electrochemically reduce N2 to NH3 at a substantial way due to the competitive route of H+ reduction to H2 in water. However, some materials were found to be excellent for electrochemical production of H2 from water. As a result, two research papers in good level peer reviewed journals were published based on our findings. Recommendation to the Siemens about the electrochemical synthesis of ammonia compared to H2 in the presence of N2/water was therefore made. |
| Start Year | 2016 |
| Description | electrochemical synthesis of ammonia using modified nafion |
| Organisation | Science and Technologies Facilities Council (STFC) |
| Country | United Kingdom |
| Sector | Public |
| PI Contribution | This was a one- year feasibility research funded under IUK to investigate the electrochemical synthesis of ammonia at low temperatures and pressures from Nitrogen and H2/water. The focus of this study was on the use of Nafion as the electrolyte material to investigate (a) Sm-based perovskites (SFCN); (b) metallic alloy nanoparticles as electrode materials. and to optimize ammonia production at high rate with high Faraday efficiency in interactive manner in parallel with theoretical modelling (STFC on the modelling; Siemens, plc for commercial exploitation). . The work at Oxford were divided into 3 sub-work packages. • WP2.1. The focus was on the study of SmFe0.7Cu0.3-xNixO3 (SFCN) electrode, the reactants were N2 and H2. Different ratios (x) on current efficiency for electrochemical production of ammonia were explored. • WP2.2. The focus was on the study of metallic alloy (Co3Mo3N and Ni2Mo3N or similar) electrodes and the reactants were N2 and H2. • WP2.3. The focus was Nafion electrolyte also with metallic alloy electrodes, but the reactants were extended to include H2O as the proton source. |
| Collaborator Contribution | STFC took on the modelling aspects of the catalytic results by establishment of an efficient and re-usable modeling methodology work flow. They provided information on the Sm2-xSrxNiO4 and SmFe0.7Cu0.3-xNixO3 systems with different amounts of substitution, e.g. bulk structure, surface properties and potential reactive centres and carried out a systemtic theoretical comparison. The work was then extended from the ceramic systems to alloy based systems. The role(s) of Siemens, plc was to manage the project to deliver the project milestones within agreed time, cost and quality limits and they assessed the commercial feasibility of the technology that was investigated within the project. |
| Impact | (1) the construction of a dedicated bench - scale electrochemical setup was designed and built at the University of Oxford; (2) successfully synthesised and evaluated the performance of two types of cathode catalysts for the reduction of N2 to NH3 in a Nafion - based solid-state electrochemical cell, namely SmFe0.7Cu0.3-xNixO3 (SFCN) and CoMoN3.(3) Although almost identical materials with similar characteristics were made with reference to literature, it was unfortunate that the performances were far below those claimed by the literature. (4) New promising Ag based nanoparticles for both electrochemical H2 production and ammonia production was found instead |
| Start Year | 2006 |
| Description | electrochemical synthesis of ammonia using modified nafion |
| Organisation | Siemens AG |
| Country | Germany |
| Sector | Private |
| PI Contribution | This was a one- year feasibility research funded under IUK to investigate the electrochemical synthesis of ammonia at low temperatures and pressures from Nitrogen and H2/water. The focus of this study was on the use of Nafion as the electrolyte material to investigate (a) Sm-based perovskites (SFCN); (b) metallic alloy nanoparticles as electrode materials. and to optimize ammonia production at high rate with high Faraday efficiency in interactive manner in parallel with theoretical modelling (STFC on the modelling; Siemens, plc for commercial exploitation). . The work at Oxford were divided into 3 sub-work packages. • WP2.1. The focus was on the study of SmFe0.7Cu0.3-xNixO3 (SFCN) electrode, the reactants were N2 and H2. Different ratios (x) on current efficiency for electrochemical production of ammonia were explored. • WP2.2. The focus was on the study of metallic alloy (Co3Mo3N and Ni2Mo3N or similar) electrodes and the reactants were N2 and H2. • WP2.3. The focus was Nafion electrolyte also with metallic alloy electrodes, but the reactants were extended to include H2O as the proton source. |
| Collaborator Contribution | STFC took on the modelling aspects of the catalytic results by establishment of an efficient and re-usable modeling methodology work flow. They provided information on the Sm2-xSrxNiO4 and SmFe0.7Cu0.3-xNixO3 systems with different amounts of substitution, e.g. bulk structure, surface properties and potential reactive centres and carried out a systemtic theoretical comparison. The work was then extended from the ceramic systems to alloy based systems. The role(s) of Siemens, plc was to manage the project to deliver the project milestones within agreed time, cost and quality limits and they assessed the commercial feasibility of the technology that was investigated within the project. |
| Impact | (1) the construction of a dedicated bench - scale electrochemical setup was designed and built at the University of Oxford; (2) successfully synthesised and evaluated the performance of two types of cathode catalysts for the reduction of N2 to NH3 in a Nafion - based solid-state electrochemical cell, namely SmFe0.7Cu0.3-xNixO3 (SFCN) and CoMoN3.(3) Although almost identical materials with similar characteristics were made with reference to literature, it was unfortunate that the performances were far below those claimed by the literature. (4) New promising Ag based nanoparticles for both electrochemical H2 production and ammonia production was found instead |
| Start Year | 2006 |
| Description | A number of invited presentations was made through international conferences |
| Form Of Engagement Activity | A talk or presentation |
| Part Of Official Scheme? | No |
| Geographic Reach | International |
| Primary Audience | Professional Practitioners |
| Results and Impact | A series of invited presentations was made in the international conferences which includes ammonia events 2017, 2018 in Holland; NSFC-RSC & Chemical Science Symposia in Harbin, China (2018) and others. more than 300 delegates including academics, policy makers and industrialists and economists gathered to discuss the synthesis of ammonia from N2/H2O concerning green energy and environment. These conferences sparked questions and discussion afterwards, and there were reports from international organizations such as RSC, NSFC and CSIRO, etc. |
| Year(s) Of Engagement Activity | 2017,2018,2019 |