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Issue 8, 2017
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The mechanism of transmethylation in anisole decomposition over Brønsted acid sites: density functional theory (DFT) study

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Abstract

In this work, the mechanism and intrinsic reaction energy barriers of transmethylation, as the initial stage of catalytic and non-catalytic anisole decomposition, were investigated by Density Functional Theory (DFT). Molecular analyses indicated that methyl free radical transfer occurred in the absence of a catalyst, and the catalytic transmethylation over Brønsted acid sites was considered based on a dual electrophilic attack mechanism with protonation and carbocation substitution. Reaction modelling for the formation of methyl-containing compounds in both non-catalytic and catalytic anisole decomposition indicated that the energy barriers were significantly decreased in the presence of a catalyst by 60 kcal mol−1 at the most in the case of o-cresol. The results also revealed that the intrinsic transmethylation orientation preferred the ortho- and para-positions on the acceptor compounds containing oxygen-rich substituents due to their large electronegativity, and the lowest energy barrier was observed in the case of transmethylation towards the para-position of the cresol molecule (54.1 kcal mol−1).

Graphical abstract: The mechanism of transmethylation in anisole decomposition over Brønsted acid sites: density functional theory (DFT) study

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Publication details

The article was received on 07 Jun 2017, accepted on 15 Aug 2017 and first published on 15 Aug 2017


Article type: Paper
DOI: 10.1039/C7SE00280G
Citation: Sustainable Energy Fuels, 2017,1, 1788-1794
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    The mechanism of transmethylation in anisole decomposition over Brønsted acid sites: density functional theory (DFT) study

    J. Zhang, B. Fidalgo, A. Kolios, D. Shen and S. Gu, Sustainable Energy Fuels, 2017, 1, 1788
    DOI: 10.1039/C7SE00280G

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