Confinement-Driven Dimethyl Ether Carbonylation in Mordenite Zeolite as an Ultramicroscopic Reactor

作者：Wei Chen, Zhiqiang Liu, Xianfeng Yi, Anmin Zheng · 发表于：Accounts of Chemical Research · 年份：2024 · DOI：10.1021/acs.accounts.4c00389 · 被引用次数：17 · 研究领域：Zeolite Catalysis and Synthesis、Asymmetric Hydrogenation and Catalysis、Catalysis and Oxidation Reactions

Conspectus The conversion of C1 molecules to methyl acetate through the carbonylation of dimethyl ether in mordenite zeolite is an appealing reaction and a crucial step in the industrial coal-to-ethanol process. Mordenite zeolite has large 12-membered-ring (12MR) channels (7.0 × 6.5 Å 2 ) and small 8MR channels (5.7 × 2.6 Å 2 ) connected by a side pocket (4.8 × 3.4 Å 2 ), and this unique pore architecture supplies its high catalytic activity to the key step of carbonylation. However, the reaction mechanism of carbonylation in mordenite zeolite is not thoroughly established in that it is able to explain all experimental phenomena and improve its industrial applications, and the classical potential energy surface exerted by static density function theory calculations cannot reflect the reaction kinetics under realistic conditions because the diffusion kinetics of bulk DME (kinetic dimeter: 4.5 Å) and methyl acetate (MA, kinetic dimeter: 5.5 Å) were not well considered and their restricted diffusion in the narrow side pocket and 8MR channels may greatly alter the integrated kinetics of DME carbonylation in mordenite zeolite. Moreover, the precise illustration of the dynamic behaviors of the ketene intermediate and its derivatives (surface acetate and acylium ion) confined within various voids in mordenite has not been effectively portrayed. Advanced ab initio molecular dynamics (AIMD) simulations with or without the acceleration of enhanced sampling methods provide tremendous op...