A comparison of the reactivity of the lattice nitrogen in tungsten substituted Co3Mo3N and Ni2Mo3N
A comparison of the reactivity of the lattice nitrogen in tungsten substituted Co3Mo3N and Ni2Mo3N
The effect of the partial substitution of Mo with W in Co3Mo3N and Ni2Mo3N on ammonia synthesis activity and lattice nitrogen reactivity has been investigated. This is of interest as the coordination environment of lattice N is changed by this process. When tungsten was introduced into the metal nitrides by substitution of Mo atoms, the catalytic performance was observed to have decreased. As expected, Co3Mo3N was reduced to Co6Mo6N under a 3 : 1 ratio of H2/Ar. Co3Mo2.6W0.4N was also shown to lose a large percentage of lattice nitrogen under these conditions. The bulk lattice nitrogen in Ni2Mo3N and Ni2Mo2.8W0.2N was unreactive, demonstrating that substitution with tungsten does not have a significant effect on lattice N reactivity. Computational calculations reveal that the vacancy formation energy for Ni2Mo3N is more endothermic than Co3Mo3N. Furthermore, calculations suggest that the inclusion of W does not have a substantial impact on the surface N vacancy formation energy or the N2 adsorption and activation at the vacancy site.
ammonia synthesis, DFT, Mars-van Krevelen, metal nitride, nitrogen vacancies
Al Sobhi, Samia
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AlShibane, Ihfaf
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Catlow, C. Richard A.
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Daisley, Angela
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Hargreaves, Justin S.J.
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Hector, Andrew L.
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Higham, Michael D.
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Zeinalipour-Yazdi, Constantinos D.
a2fdde38-2e52-49c5-b1f2-247244999505
22 November 2023
Al Sobhi, Samia
f9e2d187-4c9f-40db-a69d-5e257a35f56d
AlShibane, Ihfaf
69dbd56b-2526-4c62-901b-d4af30703b64
Catlow, C. Richard A.
50b88125-9415-4b37-9146-af6783e42510
Daisley, Angela
88540ea0-e9a9-4757-a77d-40e219985875
Hargreaves, Justin S.J.
d95754e7-6e2d-4c98-b151-b6b73b0f8024
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Higham, Michael D.
7ec9b048-438f-4c02-8931-509c7f0b94d4
Zeinalipour-Yazdi, Constantinos D.
a2fdde38-2e52-49c5-b1f2-247244999505
Al Sobhi, Samia, AlShibane, Ihfaf, Catlow, C. Richard A., Daisley, Angela, Hargreaves, Justin S.J., Hector, Andrew L., Higham, Michael D. and Zeinalipour-Yazdi, Constantinos D.
(2023)
A comparison of the reactivity of the lattice nitrogen in tungsten substituted Co3Mo3N and Ni2Mo3N.
ChemSusChem, 16 (22), [e202300945].
(doi:10.1002/cssc.202300945).
Abstract
The effect of the partial substitution of Mo with W in Co3Mo3N and Ni2Mo3N on ammonia synthesis activity and lattice nitrogen reactivity has been investigated. This is of interest as the coordination environment of lattice N is changed by this process. When tungsten was introduced into the metal nitrides by substitution of Mo atoms, the catalytic performance was observed to have decreased. As expected, Co3Mo3N was reduced to Co6Mo6N under a 3 : 1 ratio of H2/Ar. Co3Mo2.6W0.4N was also shown to lose a large percentage of lattice nitrogen under these conditions. The bulk lattice nitrogen in Ni2Mo3N and Ni2Mo2.8W0.2N was unreactive, demonstrating that substitution with tungsten does not have a significant effect on lattice N reactivity. Computational calculations reveal that the vacancy formation energy for Ni2Mo3N is more endothermic than Co3Mo3N. Furthermore, calculations suggest that the inclusion of W does not have a substantial impact on the surface N vacancy formation energy or the N2 adsorption and activation at the vacancy site.
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ChemSusChem - 2023 - Al Sobhi - A Comparison of the Reactivity of the Lattice Nitrogen in Tungsten Substituted Co3Mo3N and
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e-pub ahead of print date: 13 September 2023
Published date: 22 November 2023
Additional Information:
Funding Information:
. The authors would like to acknowledge the EPSRC for the research grants EP/T027851/1, EP/T028416/1 and EP/T028629/1 for the financial support of this project, and the UK Catalysis Hub Consortium (funded by EPSRC (Grants EP/R026815/1)) for the provision of additional resources. The authors acknowledge the STFC (SCARF) and UK National Supercomputing Service (ARCHER2) for the provision of computational resources, the latter enabled via membership of the MCC (EP/L000202)
Funding Information:
The authors would like to acknowledge the EPSRC for the research grants EP/T027851/1, EP/T028416/1 and EP/T028629/1 for the financial support of this project, and the UK Catalysis Hub Consortium (funded by EPSRC (Grants EP/R026815/1)) for the provision of additional resources. The authors acknowledge the STFC (SCARF) and UK National Supercomputing Service (ARCHER2) for the provision of computational resources, the latter enabled via membership of the MCC (EP/L000202).
Publisher Copyright:
© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.
Keywords:
ammonia synthesis, DFT, Mars-van Krevelen, metal nitride, nitrogen vacancies
Identifiers
Local EPrints ID: 483734
URI: http://eprints.soton.ac.uk/id/eprint/483734
ISSN: 1864-5631
PURE UUID: 29711cc4-4751-4638-b140-00c49a4294c8
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Date deposited: 03 Nov 2023 18:03
Last modified: 06 Jun 2024 01:36
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Contributors
Author:
Samia Al Sobhi
Author:
Ihfaf AlShibane
Author:
C. Richard A. Catlow
Author:
Angela Daisley
Author:
Justin S.J. Hargreaves
Author:
Michael D. Higham
Author:
Constantinos D. Zeinalipour-Yazdi
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