文献类型：期刊文献

英文题名：Dual Microenvironment Modulation of Pd Nanoparticles in Covalent Organic Frameworks for Semihydrogenation of Alkynes

作者：Guo, Mingchun[1];Meng, Qiangqiang[2];Chen, Wenyao[3];Meng, Zheng[1];Gao, Ming-Liang[1];Li, Qunxiang[2];Duan, Xuezhi[3];Jiang, Hai-Long[1]

机构：[1]Univ Sci & Technol China, Hefei Natl Res Ctr Phys Sci Microscale, Collaborat Innovat Ctr Chem Energy Mat iChEM, Dept Chem, Hefei 230026, Anhui, Peoples R China;[2]Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Anhui, Peoples R China;[3]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2023

卷号：62

期号：26

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20232114114979);WOS:【SCI-EXPANDED(收录号:WOS:000988907300001)】；

基金：Acknowledgments This work was supported by the National Key Research and Development Program of China (2021YFA1500402), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0450302), National Natural Science Foundation of China (U22A20401, 22161142001, and 22101269), and Fundamental Research Funds for the Central Universities (WK3450000007, WK2060000038).

语种：英文

外文关键词：Covalent-Organic Frameworks; Heterogeneous Catalysis; Hydrogenation; Metal Nanoparticles; Microenvironment Modulation

摘要：The chemical microenvironment modulation of metal nanoparticles (NPs) holds promise for tackling the long-lasting challenge of the trade-off effect between activity and selectivity in catalysis. Herein, ultrafine PdCu2 NPs incorporated into covalent organic frameworks (COFs) with diverse groups on their pore walls have been fabricated for the semihydrogenation of alkynes. The Cu species, as the primary microenvironment of Pd active sites, greatly improves the selectivity. The functional groups as the secondary microenvironment around PdCu2 NPs effectively regulate the activity, in which PdCu2 NPs encapsulated in the COF bearing -CH3 groups exhibit the highest activity with >99 % conversion and 97 % selectivity. Both experimental and calculation results suggest that the functional group affects the electron-donating ability of the COFs, which successively impacts the charge transfer between COFs and Pd sites, giving rise to a modulated Pd electronic state and excellent catalytic performance.