文献类型：期刊文献

英文题名：Substrate-Dependent Selectivity in Alkyne Semihydrogenation Over a Hydrogen-Competent Pd3Sn2 Intermetallic Catalyst

作者：Liang, Yijing[1];Zhu, Ningchao[1];Jing, Yundao[1];Ge, Xiaohu[1];Zhang, Jing[1];Qian, Gang[1];Cao, Yueqiang[1,2];Zhou, Xinggui[1,2];Chen, De[1,2,3];Yuan, Weikang[1];Duan, Xuezhi[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai, Peoples R China;[3]Norwegian Univ Sci & Technol, Dept Chem Engn, Trondheim, Norway

年份：2026

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20262120777142);WOS:【SCI-EXPANDED(收录号:WOS:001769602700001)】；

基金：This work was financially supported by the National Key R&D Program of China (2022YFA1503804), the Natural Science Foundation of China (22538004, 22332003, 22478106, and 22408097), the Chang Jiang Scholars Program of the Ministry of Education of China (T2022163), the Natural Science Foundation of Shanghai (24ZR1415300), Shanghai Rising-star Program (23QA1401900), the Science and Technology Commission of Shanghai Municipality Strategic Frontier Dedicated Project on Green Fuels (25DP30GF210), the Science and Technology Commission of Shanghai Municipality Key Technology R&D Plan program (25DZ3000100) and Key Basic Research Program (23JC1403300), the Guangxi Science and Technology Program (LT2504240025-3), and Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404). We thank the Shanghai Synchrotron Radiation Facility of BL14W1 (https://cstr.cn/31124.02.SSRF.BL14W1) for the assistance on GIWAXS measurements.

语种：英文

外文关键词：configuration matching; hydrogen dissociation; near-surface site; Pd-Sn intermetallic; propyne semihydrogenation

摘要：A recurring challenge in heterogeneous hydrogenation is to maintain rapid H2 activation while preventing the product from undergoing overhydrogenation. Site isolation can weaken adsorption but frequently compromises hydrogen competence, and selectivity is often presumed transferable across closely related substrates. Here we establish a substrate-dependent selectivity framework on Pd-Sn intermetallic catalysts by integrating theory-guided site identification with experimental validation. Theoretical calculations reveal that Pd3Sn2 hosts a distinctive surface structure in which Sn-bridged Pd-Pd dual sites cooperate with adjacent near-surface Pd to dissociate H2 readily, while methyl substitution in C3 intermediates weakens pi-binding and kinetically favors propylene desorption over further hydrogenation. Guided by these predictions, phase-pure Pd3Sn, Pd3Sn2, and PdSn2 intermetallic catalysts with comparable particle sizes were synthesized and verified by comprehensive characterizations including aberration-corrected electron microscopy and x-ray absorption spectroscopy. Under excess-propylene conditions, the Pd3Sn2 catalyst achieves 98.0% propylene selectivity at 100% propyne conversion, whereas the Pd and Pd3Sn catalysts suffer severe overhydrogenation and the PdSn2 catalyst is intrinsically sluggish. Notably, the Pd3Sn2 catalyst performs poorly for acetylene hydrogenation, leading to significant ethane formation via overhydrogenation of both newly formed and co-fed ethylene. Complementary kinetic evidence supports the proposed mechanism by quantifying hydrogen activation competence and product residence on the intermetallic surfaces.