Theoretical insights into the nature of synergistic enhancement in bimetallic CoTiAlPO-5 catalysts for ammonia activation
Theoretical insights into the nature of synergistic enhancement in bimetallic CoTiAlPO-5 catalysts for ammonia activation
Bimetallic catalytic synergy, the concurrent action of two different metal ions in the same material, has resulted in improved efficiency in many catalytic systems and for a range of chemical processes. Via a computational mechanistic study, we investigate the catalytic benefits of the bimetallic CoTiAlPO-5 material in comparison to the monometallic CoAlPO-5 system, on the activation of NH3. The presence of Ti in a framework site adjacent to Co stabilises the Co(II) oxidation state, and increases the Co(III)/Co(II) reduction potential. We show that this change lowers the activation barrier for the homolytic H extraction from NH3 by Co(III), from 162 kJ mol−1 in the monometallic CoAlPO-5 catalyst to 140 kJ mol−1 in the bimetallic CoTiAlPO-5 (175 and 111 kJ mol−1 respectively when considering both dispersion and free energy corrections). Elucidation of mechanistic details through computational studies can make significant contributions to the rational design of catalytic materials.
3474-3480
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
McColl, Kenneth
7d123d17-913c-47f3-9950-830f491069c5
Corà, Furio
42617dab-0825-45cd-9a00-9e250cc8777b
Levy, Alan B.
b6f54b52-0292-413b-a36f-d056e4d1204f
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
21 August 2017
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
McColl, Kenneth
7d123d17-913c-47f3-9950-830f491069c5
Corà, Furio
42617dab-0825-45cd-9a00-9e250cc8777b
Levy, Alan B.
b6f54b52-0292-413b-a36f-d056e4d1204f
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Potter, Matthew, McColl, Kenneth, Corà, Furio, Levy, Alan B. and Raja, Robert
(2017)
Theoretical insights into the nature of synergistic enhancement in bimetallic CoTiAlPO-5 catalysts for ammonia activation.
Catalysis Science & Technology, 7 (16), .
(doi:10.1039/c7cy00965h).
Abstract
Bimetallic catalytic synergy, the concurrent action of two different metal ions in the same material, has resulted in improved efficiency in many catalytic systems and for a range of chemical processes. Via a computational mechanistic study, we investigate the catalytic benefits of the bimetallic CoTiAlPO-5 material in comparison to the monometallic CoAlPO-5 system, on the activation of NH3. The presence of Ti in a framework site adjacent to Co stabilises the Co(II) oxidation state, and increases the Co(III)/Co(II) reduction potential. We show that this change lowers the activation barrier for the homolytic H extraction from NH3 by Co(III), from 162 kJ mol−1 in the monometallic CoAlPO-5 catalyst to 140 kJ mol−1 in the bimetallic CoTiAlPO-5 (175 and 111 kJ mol−1 respectively when considering both dispersion and free energy corrections). Elucidation of mechanistic details through computational studies can make significant contributions to the rational design of catalytic materials.
Text
C7CY00965H
- Accepted Manuscript
More information
Accepted/In Press date: 26 June 2017
e-pub ahead of print date: 27 June 2017
Published date: 21 August 2017
Identifiers
Local EPrints ID: 412100
URI: http://eprints.soton.ac.uk/id/eprint/412100
ISSN: 2044-4753
PURE UUID: 4b0a09a7-aaf7-4cea-88a3-0f2ef932b527
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Date deposited: 11 Jul 2017 09:43
Last modified: 18 Feb 2021 17:16
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Contributors
Author:
Kenneth McColl
Author:
Furio Corà
Author:
Alan B. Levy
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