First principles design of novel ammonia synthesis catalysts

Lead Research Organisation: University College London
Department Name: Chemistry

Abstract

The development of the Haber Bosch Process for the synthesis of ammonia on an industrial scale was one of the major achievements of the 20th Century. It can be directly credited with sustaining the global population through the provision of an accessible route to synthetic fertilizers. The process is based upon the reaction of pure N2 and H2 feedstreams over a promoted iron based catalyst. It is operated at high pressure (>100 atmospheres) and moderate temperature and the process as a whole currently accounts for a significant proportion of global energy demand (>1%). In this research, we are attempting to develop alternative catalysts which will contribute to energy savings by facilitating the reaction at lower reaction temperatures (where there is a thermodynamic advantage.) The approach to be taken will involve a mixture of computational design and experimental testing and is based upon previous studies of metal nitride catalysts which exhibit interesting activity for ammonia synthesis. Metal nitrides potentially contain "activated" nitrogen within their structure and it is the reactivity of this lattice nitrogen which which could be the key to their high activity. Using computational modelling, understanding of experimental results will be obtained and will be extended to the identification of nitride materials of potential high catalytic activity. In parallel laboratory experiments, the identified materials will be synthesised and tested and the results fed back into the computational modelling to provide improved understanding. In this way, optimal catalyst formulations will be identified and these will be prepared and tested under industrially relevant ammonia synthesis conditions and the results will be compared to those from conventional industrially applied iron based catalysts.

Publications

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Zeinalipour-Yazdi C (2015) Nitrogen Activation in a Mars-van Krevelen Mechanism for Ammonia Synthesis on Co 3 Mo 3 N in The Journal of Physical Chemistry C

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Zeinalipour-Yazdi C (2016) DFT-D3 Study of Molecular N 2 and H 2 Activation on Co 3 Mo 3 N Surfaces in The Journal of Physical Chemistry C

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Zeinalipour-Yazdi C (2018) Low-T Mechanisms of Ammonia Synthesis on Co 3 Mo 3 N in The Journal of Physical Chemistry C

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Zeinalipour-Yazdi CD (2018) On the possibility of an Eley-Rideal mechanism for ammonia synthesis on MnN (x = 1)-(111) surfaces. in Physical chemistry chemical physics : PCCP

 
Title Exhibition with the title: Science in Arts and the Art of Science 
Description The exhibition consisted of 8 framed images that were previous submissions by Dr. Zeinalipour to various Art and Science Competitions. Each image was framed in a silver metallic frame with dimensions A3, accompanied with a paragraph and title to describe the image. The title of the images presented was 1) ammonia synthesis 2) catalysts 3) crotonaldehyde oxidation 4) arbor vitae 5) the double helix 6) cell culture 7) human network 8) sphere-in-contact 
Type Of Art Artistic/Creative Exhibition 
Year Produced 2015 
Impact This exhibition prepared and presented by Dr. Constantinos Zeinalipour-Yazdi as part of the Mediterranean Science Festival 2015. This was general public event that took place in Limassol between December 3-6, 2015. There was a total of 2300 students and a total of 9300 visitors that visited the festival. Dr. Zeinalipour was there for the whole duration of the Festival, presenting a Science and art exhibition with the title: "Science in Arts and the art of science" that consisted of 8 framed images with a paragraph and title to describe the image. The title of the images presented was, ammonia synthesis, catalysts, crotonaldehyde oxidation, arbor vitae, the double helix, cell culture, human network, sphere-in-contact. Some of the images presented were from cover articles that Dr. Zeinalipour has published while funded through this EPSRC project. For example the image with the title "ammonia synthesis" was a cover article we had on the Journal of Physical Chemistry C. The exhibition was presented either to small group of students and to general public that visiting the Festival. The festival consistent of scientific activities for the general public hall, exhibitions and various scientific talks. 
URL https://www.facebook.com/MedScienceFestival/
 
Description We have shown that the surfaces of transition metal nitrides provide effective sites for reactivity in ammonia synthesis and our work is now leading to predictive modelling relating to new materials. Furthermore, we have now modeled via periodic DFT calculations the complete mechanisms of ammonia synthesis on cobalt molybdenum nitride, which is one of the most active catalysts for ammonia synthesis at ambient temperature. We found that there are two mechanism in which ammonia synthesis can proceed, the first is a Langmuir - Hinshelwood mechanism and the second an Eley - Rideal / Mars van Krevelen mechanism. The later mechanism is a novel mechanism where surface activated nitrogen at nitrogen vacancies reacts directly with hydrogen coming from the gas phase. This new mechanism for ammonia synthesis has lower barriers than the conventional LH mechanism and it suggests that the catalytic activity will be high if the number of nitrogen vacancies is kept high. This can be achieved by annealing of the catalysts in a 2-phase operation of the catalytic reactor.
Exploitation Route Apart from the fact that our project continues in collaboration with our experimental colleagues, we anticipate that the new mechanism found for ammonia synthesis may stimulate the uptake by technology innovators to design a new low-temperature ammonia synthesis device that is based on a metal nitride as the catalyst (e.g. Co3Mo3N), MnxNy). Our results will be presented this month at Johnson Matthey which is UK's largest producer of catalysts for the ammonia synthesis reaction and we anticipate further collaboration with them. In general the mechanism of the reaction can be built into a kinetic model and be used to predict the process conditions (e.g. T, feedstream concentration , P) which will result in highest conversion of molecular nitrogen (N2) and hydrogen (H2) into ammonia (NH3). This technical aspect are crucial for the development of an ammonia synthesis pilot plant that operates at lower temperatures and pressures.
Sectors Chemicals,Energy,Environment

URL https://pubs.acs.org/doi/10.1021/acs.jpcc.7b12364
 
Description The work is of growing interest in UK and international industry. This can be seen by a new wave of research output in the scientific literature that is now trying to find new catalysts for ammonia synthesis that can operate at milder conditions (lower temperature and pressure), for the development of small scale pilot plants. Building highly-efficient ammonia plants that run on renewable energy is the ultimate ambition of such research efforts in the UK, US and Japan, mostly. Our research impact was mainly by modelling the reaction mechanism of ammonia synthesis on cobalt molybdenum nitride which will be crucial for the development of kinetic models which can guide the design of new ammonia synthesis pilot plants. Our results have been published open access in the Journal of Physical Chemistry which is ranked first among various physical chemistry journals and is freely available from their website.
First Year Of Impact 2018
Sector Chemicals,Energy,Environment,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description Collaboration with Dr. Hargreaves group at University of Glasgow 
Organisation University of Glasgow
Department School of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution Our contributions to this collaboration has been mainly to acquire High-Performance-Computing resources through peer-reviewed grant proposals, to peform DFT simulations that compliment experimental findings by the group experimental group at the University of Glasgow.
Collaborator Contribution The collaborators have catalyst screening expertise and we assist their experimental efforts with computational modelling of catalytic reaction mechanisms on the relevant materials. We have so far obtained computer resources to study three materials, MnN, TaxNy and Co3Mo3N. Recently we received through a presentation given at the Materials Chemistry Consortium (MCC) meeting in Harwell (Feb 21) 17000 GBP worth of computer time to further model the reaction mechanism for ammonia synthesis on Cobalt molybdenum nitride and other related materials.
Impact This is a multi-disciplinary collaboration between an experimental heterogeneous catalysis group from the University of Glasgow and a computational materials chemistry group from UCL. In this collaboration we have the participation of three Universities, University College London (Chemistry), University of Manchester (Physics and Astronomy) and University of Glasgow (Chemistry). This collaboration has already lead to 1 peer-reviewed paper in a high-impact journal and two more that are in preparation. Members from this collaboration have so far delivered 6 talks at international conferences, two of which were invited. There have been a total of 6 poster presentations at major conferences and one Exhibition at a Science Festival. Outcomes: Peer-Reviewed Journal Publications: (1) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, C.R.A. Catlow, Nitrogen Activation in a Mars-van Krevelen Mechanism for Ammonia Synthesis on Co3Mo3N. The Journal of Physical Chemistry C, 119, 28368-28376, 2015 Talks at International Conferences: (2) C.R.A. Catlow, W.R. Flavell, J.S.J. Hargreaves, M.A. Leontiadou, A.R. McFarlane, H. Radtke, C.D. Zeinalipour-Yazdi, Lattice nitrogen reactivity in Co3Mo3N catalysts - understanding the role of surface structure and composition through application of depth resolved XPS and computational modelling, American Chemical Society meeting, San Diego, Mar. 13-17, 201 (accepted talk) (3) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, C.R.A Catlow, American Chemical Society meeting, San Diego, Mar. 13-17, 2016 (accepted talk) (4) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, CRA Catlow, Study of the Mars - van Krevelen Mechanism for Ammonia Synthesis on Co3Mo3N (111)-surfaces, American Chemical Society meeting, San Diego, March 13-17, 2016 (5) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, CRA Catlow, Molecular nitrogen activation at nitrogen vacancies on Co3Mo3N-(111) surfaces, N2 activation workshop, University of Glasgow, Feb 2-3, 2016 (6) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, C.R.A. Catlow, Ammonia Synthesis via Mars - Van Krevelen Mechanism: Adsorption and Activation of N2 on Co3Mo3N, UK Catalysis Conference 2016, Loughborough, Jan 6-8, 2016 (7) S. Laassiri, C.D. Zeinalipour-Yazdi, C.R.A. Catlow, J.S.J. Hargreaves, Ammonia Synthesis: Development of Novel Heterogeneous Catalysts Operating Via Mars-Van Krevelen Type Mechanism, 2015 AIChe Annual Meeting, Salt Lake City, Nov. 8-13, 2015 Poster Presentations (8) S. Laassiri, C.D. Zeinalipour-Yazdi, C.R.A. Catlow, J.S.J. Hargreaves, Reactivity of lattice nitrogen in tantalum nitride materials, UK Catalysis Conference, Jan 6-8, Loughborough, 2016 (9) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, CRA Catlow, Ammonia Synthesis via Mars - van Krevelen mechanism: Adsorption and Activation of N2 on Co3Mo3N 10th Thomas Young Centre Anniversary Symposium, Feb. 17-19, London, 2016 (10) C.D. Zeinalipour-Yazdi, J.S.J. Hargreaves, C.R.A. Catlow, Effect of Nitrogen Vacancies on the Catalytic and Magnetic Properties of Cobalt and Iron Molybdenum Nitrides, SURFCAT meeting, Sept. 18th, London, 2015
Start Year 2014
 
Description Collaboration with Prof. Wendy Flavell group from the University of Manchester 
Organisation University of Manchester
Country United Kingdom 
Sector Academic/University 
PI Contribution Obtained HPC resources through competitive grants to perform simulations using DFT to study stability as a function of surface composition and termination. Developed algorithms for the depth profiling of materials.
Collaborator Contribution This group brought expertise in depth-profiling of catalytic materials via XPS. They have examined the surface structure of Co3Mo3N, which is a very active catalyst for ammonia synthesis under in situ conditions. Contributions in understanding the role and surface structure and composition of catalyst through application of depth resolved X-Ray Photoelectron Spectroscopy (XPS) to catalysts
Impact This is a multi-disciplinary collaboration between a surface analytical chemistry group from the University of Manchester (Physics and Astronomy), a catalysts screening group from the University of Glasgow (Chemistry) and a computational materials chemistry group from the University College London (Chemistry). This collaboration has already lead to 1 peer-reviewed paper in a high-impact journal and two more that are in preparation. Members from this collaboration have so far delivered 6 talks at international conferences, two of which were invited. There have been a total of 6 poster presentations at major conferences and one Exhibition at a the Mediterranean Science Festival. In particular we co-author in an invited talk at the ACS meeting in California which will be submitted as a publication. The title of the talk is "Lattice nitrogen reactivity in Co3Mo3N catalysts - understanding the role of surface structure and composition through application of depth resolved XPS and computational modelling" and the authors are C R A Catlow, W R Flavell, J S J Hargreaves, M A Leontiadou, A R McFarlane, H Radtke, C Zeinalipour-Yazdi
Start Year 2015
 
Description 2 invited talks at N2 activation workshop at UGlasgow 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Prof. Richard Catlow and Dr. Constantinos Zeinalipour-Yazdi presented both a talk at 'the N2 activation workshop' organized by Dr. Justin Hargreaves at the University of Glasgow. The title of the talks were " Computer Modelling as a Tool in Catalytic Science " and "N2 activation on Co3Mo3N". The workshop consisted of about 35 invited participants both from industry and academia and had an impact on future collaborations and publications with respect to ammonia synthesis research internationally.
Year(s) Of Engagement Activity 2016
 
Description Group talk at University of Glasgow 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos Zeinalipour-Yazdi presented a talk with the title: "Molecular nitrogen activation at nitrogen vacancies on Co3Mo3N-(111) surfaces" which later lead to a publication in a peer-reviewed journal (Journal of Physical Chemistry C). In this publication me, Dr. Justin Hargreaves and Dr. Constantinos Zeinalipour-Yazdi have co-authored and it was also a cover article on the 51 issue of this journal in 2015
Year(s) Of Engagement Activity 2015
 
Description Invited talk at ACS meeting in San Diego 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact J.S. Hargreaves, A. McFarlane, C.A. Catlow, C.D. Zeinalipour-Yazdi, W.R. Flavell, M. Leontiadou, H. Radtke, Lattice nitrogen reactivity in Co3Mo3N catalysts - understanding the role of surface structure and composition through application of depth resolved XPS and computational modelling, 251 National American Chemical Society meeting, San Diego, Mar. 13-17, 2016
Year(s) Of Engagement Activity 2016
URL http://www.acs.org/content/acs/en/meetings/spring-2016.html
 
Description Invited talk at Johnson Matthey Catalysts 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Industry/Business
Results and Impact Delivered a talk about the mechanisms of ammonia synthesis on metal nitrides to Johnson Matthey employees. The discussion sparked new collaboration for an Industry-academia fellowship application. We exchanged expertise in the area of computation chemistry with respect to catalytic materials.
Year(s) Of Engagement Activity 2018
 
Description Poster Presentation at UK Catalysis Conference 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact S. Laassiri, C.D. Zeinalipour-Yazdi, C.R.A. Catlow, J.S.J. Hargreaves, Reactivity of lattice nitrogen in tantalum nitride materials, UK Catalysis Conference, Jan 6-8, Loughborough, 2016
Year(s) Of Engagement Activity 2016
 
Description Poster presentation at 12th International Materials Chemistry Conference York 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos Zeinalipour-Yazdi presentation of a poster with the title 'Enhancement of thin film magnetic properties by nitrogen-removal from Co3Mo3N and Fe3Mo3N (111)-terminated surfaces'. This poster presentation had was partially related to the current project as the materials that we studied via periodic DFT calcuations where then used to model mechanistic aspects of the ammonia synthesis mechanism.
Year(s) Of Engagement Activity 2015
 
Description Poster presentation at Joliet-Curie Conference in Cambridge 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos Zeinalipour presneted a poster with the title "Enhancement of Magnetic Properties by Nitrogen-Vacancies in Nano-films of Cobalt and Iron Molybdenum Nitride".
Year(s) Of Engagement Activity 2015
 
Description Poster presentation at TYC 10th annual symposium in London 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Dr. Constantinos Zeinalipour-Yazdi presented a poster with the title" Ammonia synthesis via Mars - van Krevelen mechanism: Adsorption and Activation of N2 on Co3Mo3N" at the Thomas Young Center annual symposium on Wednesday 17-19th February 2016. A full programme can be found here:
Year(s) Of Engagement Activity 2016
URL http://www.thomasyoungcentre.org/events/anniversary/conference-programme/
 
Description Poster presentation at the SURFCAT meeting in London 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Dr. Zeinalipour presented a poster at the SURFCAT meeeting with the title "Effect of Nitrogen Vacancies on the Catalytic and Magnetic Properties of Cobalt and Iron Molybdenum Nitrides". This meeting was very useful as one of the organizers Dr. Justin Hargreaves was there so we had a chance to look at a manuscript in which we would later co-author.
Year(s) Of Engagement Activity 2015
 
Description Presentation at EPSRC-Toucan Conference 'Shaping nanocatalysts 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Poster presentation given by Constantinos Zeinalipour at EPSRC-Toucan Conference 'Shaping nanocatalysts'. The title of the presentation was 'Low-T Mechanism of Ammonia Synthesis on Co3Mo3N' and the conference was held at King's College London between Dec 14-16, 2016
Year(s) Of Engagement Activity 2016
 
Description Presentation at UK Catalysis Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Poster presentation given by Constantinos Zeinalipour at UK Catalysis Conference. The title of the poster was 'Low-T Mechanism of Ammonia Synthesis on Co3Mo3N', an the conference was held in Loughborough between Jan 4-6, 2017.
Year(s) Of Engagement Activity 2017
 
Description Science and Art Exhibition at the Meditteranean Science Festival 2015 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Schools
Results and Impact This exhibition prepared and presented by Dr. Constantinos Zeinalipour-Yazdi as part of the Mediterranean Science Festival 2015. This was general public event that took place in Limassol between December 3-6, 2015. There was a total of 2300 students and a total of 9300 visitors that visited the festival. I was there for the almost the whole duration of the Festival (4-days) presenting a Science and art exhibition with the title: "Science in Arts and the art of science" that consisted of 8 framed images with a paragraph and title to describe the image. The title of the images presented was, ammonia synthesis, catalysts, crotonaldehyde oxidation, arbor vitae, the double helix, cell culture, human network, sphere-in-contact. Some of the images presented were from cover articles that I have published through this EPSRC project. For example the image with the title "ammonia synthesis" was a cover article we had on the Journal of Physical Chemistry C. The exhibition was presented either to small group of students and to general public that visiting the Festival. The festival consistent of scientific activities for the general public hall, exhibitions and various scientific talks.
Year(s) Of Engagement Activity 2015
 
Description Talk at AIChE Annual meeting 2015 in Salt Lake City 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact S. Laassiri, C.D. Zeinalipour-Yazdi, C.R.A. Catlow, J.S.J. Hargreaves, Ammonia Synthesis: Development of Novel Heterogeneous Catalysts Operating Via Mars-Van Krevelen Type Mechanism, 2015 AIChe Annual Meeting, Salt Lake City, Nov. 8-13, 2015
Year(s) Of Engagement Activity 2015
URL http://www.aiche.org/conferences/aiche-annual-meeting/2015
 
Description Talk at American Chemical Society Meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Talk given by Constantinos Zeinalipour to an audience mostly from academia and industry. The title of the talk was 'Study of the Mars - van Krevelen Mechanism for Ammonia Synthesis on Co3Mo3N (111)-surfaces' and the 251 National American Chemical Society meeting was held in San Diego between March 13-17, 2016
Year(s) Of Engagement Activity 2016
 
Description Talk at American Chemical Society Meeting San Diego 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos Zeinalipour-Yazdi will give at talk at the American Chemical Society Meeting which will be held in San Diego, California between March 13-17, 2016. We anticipate to receive valuable feedback about our current findings with respect to the mechanism for ammonia synthesis on one of the most active catalysts for ammonia synthesis, Co3Mo3N.
Year(s) Of Engagement Activity 2016
URL http://www.acs.org/content/acs/en/meetings/spring-2016.html
 
Description Talk at MCC meeting at Harwell/Oxfordshire 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos D. Zeinalipour-Yazdi gave a talk with the title "DFT study of ammonia synthesis mechanism on Co3Mo3N" a the Materials Chemistry Consortium meeting in order to receive 30 MkAUs of HPC resources. This meeting was in Harwell Oxfordshire on the Feb. 21 2016
Year(s) Of Engagement Activity 2016
URL http://www.ucl.ac.uk/klmc/mcc/
 
Description Talk at UK Catalysis Conference 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Dr. Constantinos Zeinalipour-Yazdi presented a talk with the title "Ammonia Synthesis via Mars - Van Krevelen Mechanism: Adsorption and Activation of N2 on Co3Mo3N". The conference participants where mainly international and national experts in catalysis research and postdoctoral students in chemistry.
Year(s) Of Engagement Activity 2016
URL https://www.qub.ac.uk/sites/UKCC2016/