文献类型：期刊文献

英文题名：Pd Ensemble Sites Tuned Local Environment of Cu Catalysts for Matching Propyne Semi-Hydrogenation

作者：Yan, Kelin[1];Ge, Xiaohu[1];Cao, Yueqiang[1];Qiang, Yuwen[1];Zhang, Jing[1];Dai, Sheng[2];Qian, Gang[1];Chen, De[3];Zhou, Xinggui[1];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Key Lab Adv Mat Joint Int Res Lab Precis Chem & Mo, Shanghai 200237, Peoples R China;[3]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2025

卷号：64

期号：19

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20251218077047);WOS:【SCI-EXPANDED(收录号:WOS:001441251900001)】；

基金：This work was financially supported by the Ministry of Science and Technology of the People's Republic of China under the Research Fund for National Key R&D Program of China (2022YFA1503804), the Natural Science Foundation of China (22478106, 22376062, and 22178100), Shanghai Rising-Star Program (23QA1401900), the Innovation Program of Shanghai Municipal Education Commission, the Shanghai Science and Technology Innovation Action Plan (22JC1403800), the Program of Shanghai Academic/Technology Research Leader (21XD1421000), the Science and Technology Commission of Shanghai Municipality (22ZR1415700), and the Fundamental Research Funds for the Central Universities. We thank the BL11B and BL14W1 XAFS beamlines of Shanghai Synchrotron Radiation Facility (SSRF) for providing beamtime.

语种：英文

外文关键词：Configuration; Ensemble sites; Local environment; Propyne semi-hydrogenation; Reaction pathway

摘要：Tailoring local environments of active sites to match targeted configuration of key species is significant for controlling reaction pathways in selective hydrogenations. Herein, differently typed Pd sites are introduced onto Cu catalysts to tune the local environment of Cu sites for controlling the configuration of semi-hydrogenation pathway of propyne hydrogenation used in production of polymer-grade propylene. Detailed structure characterizations demonstrate the controllable construction of Pd single-atom and Pd ensemble sites modified Cu surfaces and PdCu alloy via fine tuning the Pd/Cu ratios. Catalytic tests, kinetics analysis, and temperature-programmed experiments demonstrate that the presence of Pd ensemble sites on Cu surface directly catalyzes the hydrogenation of propyne that occurs on the Cu sites in other cases, and enables a facile activation for hydrogen and simultaneously promotes the desorption of propylene against its hydrogenation. Accordingly, the selectivity to target propylene is up to 95.3% at the full conversion of propyne on the corresponding Pd0.1Cu catalyst. In contrast, the C & horbar;C coupling pathway is quite facile on the Cu surface tuned by single-atom Pd sites, which is similar to that on the pristine Cu sites on the Cu catalyst, and the well-defined Pd & horbar;Cu coordination on PdCu alloy catalyst leads to facile over-hydrogenation process.