{"title":"Heterogeneous Carbonylation of Alcohols on Charge-Density-Distinct Mo-Ni Dual Sites Localized at Edge Sulfur Vacancies","authors":"Qiao Yuan, Yating Gu, Weimiao Chen, Yue Zhang, Xiangen Song, Yangming Ding, Xingju Li, Lei Zhu, Zheng Jiang, Li Yan, Jing Ma, Yunjie Ding","doi":"10.1002/anie.202411632","DOIUrl":null,"url":null,"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.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202411632","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
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.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.