文献类型：期刊文献

英文题名：Effect of R-SO2-R' ligands on the gold-based catalysts for acetylene hydrochlorination: A DFT study

作者：Yang, Jiaqi[1,2];Shen, Haitao[1,2];Yuan, Xiangqian[1,2];Zhao, Jigang[1,2]

机构：[1]East China Univ Sci & Technol, Int Joint Res Ctr Green Energy Chem Engn, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：675

外文期刊名：COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS

收录：;EI(收录号：20232914421955);WOS:【SCI-EXPANDED(收录号:WOS:001054457700001)】；

基金：This work was financially supported by National Key R & D Program (No.2017YFB0306601) .

语种：英文

外文关键词：Acetylene hydrochlorination; Acetylene self-polymerization; Sulfur-containing ligand; Gold-based catalyst; DFT calculation

摘要：Gold-based mercury-free catalysts have great potential in the industrial production of vinyl chloride. In order to further understand the factors affecting the catalytic activity, the catalytic reaction mechanisms of five kinds of sulfur-containing ligand gold-based catalysts are studied by DFT calculation at the PBE0/def2-TZVP level, and dispersion-corrected DFT-D3 is performed. The results show that the rate control step in the reaction path is the transfer of proton hydrogen. With the increase of Mulliken charges of Au and S atoms in the catalyst, the energy barrier of acetylene hydrochlorination decreases. The catalyst formed by methanesulfonic acid and AuCl3 has the lowest energy barrier of acetylene hydrochlorination (23.18 kcal/mol). Compared to AuCl3 catalyst, adding ligands can significantly reduce the products desorption energy. When the ligand has an electron-withdrawing group, the corresponding acetylene self-polymerization barrier is lower. These results provide valuable theoretical guidance for preparation of efficient sulfur-containing ligand gold-based catalysts in future.