Issue 32, 2021

QM/MM study of the reactivity of zeolite bound methoxy and carbene groups


The conversion of methanol-to-hydrocarbons (MTH) is known to occur via an autocatalytic process in zeolites, where framework-bound methoxy species play a pivotal role, especially during catalyst induction. Recent NMR and FT-IR experimental studies suggest that methoxylated zeolites are able to produce hydrocarbons by a mechanism involving carbene migration and association. In order to understand these observations, we have performed QM/MM computational investigations on a range of reaction mechanisms for the reaction of zeolite bound methoxy and carbene groups, which are proposed to initiate hydrocarbon formation in the MTH process. Our simulations demonstrate that it is kinetically unfavourable for methyl species to form on the framework away from the zeolite acid site, and both kinetically and thermodynamically unfavourable for methyl groups to migrate through the framework and aggregate around an acid site. Formation of carbene moieties was considered as an alternative pathway to the formation of C–C bonds; however, the reaction energy for conversion of a methyl to a carbene is unfavourable. Metadynamics simulations help confirm further that methyl species at the framework acid sites would be more reactive towards formed C2+ species, rather than inter-framework migration, and that the role of carbenes in the formation of the first C–C bond will be via a concerted type of mechanism rather than stepwise.

Graphical abstract: QM/MM study of the reactivity of zeolite bound methoxy and carbene groups

Supplementary files

Article information

Article type
06 Jun 2021
25 Jul 2021
First published
27 Jul 2021
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2021,23, 17634-17644

QM/MM study of the reactivity of zeolite bound methoxy and carbene groups

S. A. F. Nastase, A. J. Logsdail and C. R. A. Catlow, Phys. Chem. Chem. Phys., 2021, 23, 17634 DOI: 10.1039/D1CP02535J

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