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 molacetyl/kgcat./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.
Q. Yuan, Y. Gu, W. Chen, Y. Zhang, X. Song, Y. Ding, X. Li, L. Zhu, Z. Jiang, L. Yan, J. Ma, Y. Ding, Heterogeneous carbonylation of alcohols on charge-density-distinct mo-ni dual sites localized at edge sulfur vacancies, Angewandte Chemie International Edition, 2024, n/a, e202411632. DOI: 10.1002/anie.202411632.
