文献类型：期刊文献

英文题名：Oxygen effect on the synthesis of vinyl acetate on Pd (100) and Pd/Au (100) surfaces: A periodic DFT study

作者：Liu, Zhiqiang[1];Qiu, Pengyuan[2];Sun, Haoyang[2];Sun, Li[1];Zeng, Zuoxiang[1];Liu, Zhen[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]SINOPEC, Shanghai Res Inst Petrochem Technol, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 201208, Peoples R China

年份：2023

卷号：547

外文期刊名：MOLECULAR CATALYSIS

收录：;EI(收录号：20233014432487);WOS:【SCI-EXPANDED(收录号:WOS:001043998600001)】；

基金：This research was financially supported by the National Natural Science Foundation of China (22171084) , Shanghai Pujiang Program (18PJ1402500) , and the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-18C01) at the East China University of Science and Technology. We acknowledge the supercomputer at East China University of Science and Technology for generous computing resources.

语种：英文

外文关键词：Vinyl acetate synthesis; Oxygen effect; DFT; Reaction mechanism

摘要：Vinyl acetate is mainly produced by oxidative acetoxylation of ethylene over the Pd/Au bimetallic heterogeneous catalyst. This process requires the involvement of oxygen, but the role of oxygen has not been well studied. The oxygen effect on the synthesis of vinyl acetate is of considerable economic benefit, as the process conditions can be better optimized. In this study, the O2 adsorption and dissociation on the Pd (100) and Pd/Au (100) surfaces, the effect of the co-adsorbed O atom on the C2H4, CH3COOH and CH3COO adsorptions, and the reaction mechanism have been investigated using ab initio density functional theory (DFT) method. The calculated results suggest that the O adatoms are detrimental to the adsorption of C2H4 and CH3COO, but favorable for CH3COOH. For the reaction, the O adatoms reduce the energy barrier of CH3COOH dehydrogenation and VA formation, and increase the reaction enthalpy (more exothermic). This study provides further mechanistic insight into VA synthesis on the Pd-based catalysts.