Heterogeneous Carbonylation of Alcohols on Charge‐Density‐Distinct Mo−Ni Dual Sites Localized at Edge Sulfur Vacancies
Qiao Yuan, Yating Gu, Weimiao Chen, Yue Zhang, Xiangen Song, Yangming Ding, Yangming Ding, Xingju Li, Lei Zhu, Zheng Jiang, Yan Li, Jing Ma, Yunjie Ding, Yunjie Ding
Abstract
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.