Journal
CHEMCATCHEM
Volume 6, Issue 7, Pages 1906-1918Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201402146
Keywords
kinetics; methylation; molecular dynamics; molecular modeling; zeolites
Categories
Funding
- Research Foundation Flanders (FWO)
- Research Board of Ghent University (BOF)
- BELSPO [IAP 7/05]
- European Research Council under European Community [240483]
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Framework-bound methoxides occur as intermediates in the stepwise mechanism for zeolite-catalyzed methylation reactions. Herein, the formation of methoxides from methanol or dimethyl ether in H-ZSM-5 is investigated by a combination of static and dynamic simulations, with particular focus on the effect of additional water and methanol molecules on the mechanism and kinetics. Metadynamics simulations allow partitioning the reaction path into distinct phases. Proton transfer from the zeolite to the reactants is found to be the rate-limiting phase in the methoxide formation. Additional methanol molecules only assist the proton transfer in the methoxide formation from methanol, whereas the reaction from dimethyl ether does not benefit from methanol assistance. Once formed, methoxides are found to be as reactive toward alkene methylation as methanol and dimethyl ether.
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