Brønsted/Lewis acid sites synergistically promote the initial C–C bond formation in the MTO reaction

Abstract

The methanol-to-olefin (MTO) reaction is an active field of research due to conflicting mechanistic proposals for the initial carbon–carbon (C–C) bond formation. Herein, a new methane–formaldehyde pathway, a Lewis acid site combined with a Brønsted acid site in zeolite catalysts can readily activate dimethyl ether (DME) to form ethene, is identified theoretically. The mechanism involves a hydride transfer from Al–OCH₃ on the Lewis acid site to the methyl group of the protonated methanol molecule on the adjacent Brønsted acid site leading to synchronous formation of methane and Al–COH₂⁺ (which can be considered as formaldehyde (HCHO) adsorbed on the Al³⁺ Lewis acid sites). The strong electrophilic character of the Al–COH₂⁺ intermediate can strongly accelerate the C–C bond formation with CH₄, as indicated by the significant decrease of activation barriers in the rate-determining-step of the catalytic processes. These results highlight a synergy of extra-framework aluminum (EFAl) Lewis and Brønsted sites in zeolite catalysts that facilitates initial C–C bond formation in the initiation step of the MTO reaction via the Al–COH₂⁺ intermediate.