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

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@MoS₂ catalyst. Mechanistic analysis reveals that the Mo-Ni dual sites localized at edge sulfur vacancies of Ni@MoS₂ exhibit distinct charge density, which strongly activate CH₃OH 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@MoS₂ 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.