Heterogeneous Carbonylation of Alcohols on Charge‐Density‐Distinct Mo−Ni Dual Sites Localized at Edge Sulfur Vacancies

Abstract Alcohols carbonylation is of great importance in industry but remains a challenge to abandon the usage of the halide additives and noble metals. Here we report the realization of direct alcohols heterogeneous carbonylation to carbonyl‐containing chemicals, especially in methanol carbonylation, with a remarkable space‐time‐yield (STY) of 4.74 mol acetyl /kg cat. /h and a durable stability as long as 100 h on Ni@MoS 2 catalyst. Mechanistic analysis reveals that the Mo−Ni dual sites localized at edge sulfur vacancies of Ni@MoS 2 exhibit distinct charge density, which strongly activate CH 3 OH to break its C−O bond and non‐dissociatively activate CO. Density functional theory calculations further suggest that the low charge density in Mo−Ni, the Ni site, could significantly lower the barrier for CO migration and nucleophilic attack of methoxy species, and finally leads to the rapid formation of acetyl products. Ni@MoS 2 catalyst could also effectively realize the carbonylation of ethanol, n‐propanol and n‐butanol to their acyl products, which may demonstrate its universal application for alcohols carbonylation.