Modelling metal centres, acid sites and reaction mechanisms in microporous catalysts

O'Malley, Alexander J., Logsdail, A. J. ORCID: https://orcid.org/0000-0002-2277-415X, Sokol, A. A. and Catlow, C. R. A. ORCID: https://orcid.org/0000-0002-1341-1541 2020. Modelling metal centres, acid sites and reaction mechanisms in microporous catalysts. Faraday Discussions 188 , pp. 235-255. 10.1039/C6FD00010J

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Abstract

We discuss the role of QM/MM (embedded cluster) computational techniques in catalytic science, in particular their application to microporous catalysis. We describe the methodologies employed and illustrate their utility by briefly summarising work on metal centres in zeolites. We then report a detailed investigation into the behaviour of methanol at acidic sites in zeolites H-ZSM-5 and H-Y in the context of the methanol-to-hydrocarbons/olefins process. Studying key initial steps of the reaction (the adsorption and subsequent methoxylation), we probe the effect of framework topology and Brønsted acid site location on the energetics of these initial processes. We find that although methoxylation is endothermic with respect to the adsorbed system (by 17–56 kJ mol−1 depending on the location), there are intriguing correlations between the adsorption/reaction energies and the geometries of the adsorbed species, of particular significance being the coordination of methyl hydrogens. These observations emphasise the importance of adsorbate coordination with the framework in zeolite catalysed conversions, and how this may vary with framework topology and site location, particularly suited to investigation by QM/MM techniques

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry Cardiff Catalysis Institute (CCI)
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1359-6640
Funders:	EPSRC
Date of First Compliant Deposit:	9 September 2016
Date of Acceptance:	3 February 2016
Last Modified:	07 May 2023 11:28
URI:	https://orca.cardiff.ac.uk/id/eprint/94401

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