文献类型：期刊文献

英文题名：Mechanistic insights into propylene oxidation to acrolein over gold catalysts

作者：Lin, Bin[1];Chen, Wenyao[1];Song, Nan[1];Zhang, Zhihua[1];Wang, Qianhong[1];Du, Wei[1];Zhou, Xinggui[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：57

起止页码：39

外文期刊名：CHINESE JOURNAL OF CHEMICAL ENGINEERING

收录：;EI(收录号：20231613889580);WOS:【SCI-EXPANDED(收录号:WOS:000983792000001)】；

基金：This work was financially supported by the Research Fund for National Key Research and Development Program of China (2021YFA1501403), the Natural Science Foundation of China (22208094, 22038003, 21922803, 22178100), the Innovation Program of Shanghai Municipal Education Commission, the Program of Shanghai Academic/Technology Research Leader (21XD1421000) and the Shanghai Science and Technology Innovation Action Plan (22JC1403800)..

语种：英文

外文关键词：Acrolein formation; Oxygenated species; DFT calculations; Au surfaces; Reaction mechanism

摘要：Direct epoxidation of propylene with H2/O2, being the dream reaction for propylene oxide (PO) production, has raised wide scientific and industrial interests. Fundamentally understanding the formation mechanism of acrolein, as the main by-product of this epoxidation process, is very important to achieve the high yield of PO. In this study, we perform the spin-polarized density functional theory (DFT) calculations to investigate the reaction pathway from propylene to acrolein over two representative Au surfaces, that is, Au(1 1 1) and Au(1 0 0), which incorporates propylene adsorption, methyl hydrogen activation and acrolein formation. The results show that the oxygenated species (mainly O*, OH* and OOH*) are able to stabilize the adsorption of propylene to decrease the energy barrier for its activation. It is demonstrated that the OOH* on Au(1 1 1) surface emerges as the most easily formed oxygenated species via the H-assisted O2 dissociation, which is also the most active for the cleavage of methyl CAH bond in propylene. Furthermore, three pathways of acrolein formation activated by O*/OH*/OOH* are analyzed, in which O* is found as the key species to form acrolein. Finally, Bader charge analysis was conducted to explore the reasons behind the promotion effect of the oxygenated species. The insights reported here could be valuable in the design and optimization of gold catalysts for the direct epoxidation of propylene.(c) 2022 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.