文献类型：期刊文献

英文题名：Intermetallicization of Pd with Sn to Match Adsorption Configuration toward Highly Selective Hydrogenation

作者：Li, Wenhua[1];Ge, Xiaohu[1];Yao, Chang[1];Cao, Yueqiang[1,3];Zhang, Jing[1];Qian, Gang[1];Zhou, Xinggui[1];Chen, De[1,2];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway;[3]Minist Educ, Engn Res Ctr Resource Utilizat Carbon Containing W, Shanghai 200237, Peoples R China

年份：2025

卷号：15

期号：14

起止页码：12365

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20252918779271);WOS:【SCI-EXPANDED(收录号:WOS:001525987700001)】；

基金：This work was financially supported by the National Key R&D Program of China (2022YFA1503804), the Natural Science Foundation of China (22332003, 22478106, and 22178100), the Shanghai Rising-Star Program (23QA1401900), the Young Elite Scientists Sponsorship Program by CAST (2023QNRC001), the Open Project of Yunnan Precious Metals Laboratory Co., Ltd (YPML-2023050272), and the Fundamental Research Funds for the Central Universities. We acknowledge the BL14W1 XAFS beamline of the Shanghai Synchrotron Radiation Facility (SSRF) for providing the beamtime.

语种：英文

外文关键词：selective hydrogenation; Pd-Sn intermetallics; nitroaromatic hydrogenation; adsorption configuration; kinetics

摘要：Heterogeneous hydrogenation promoted by metal catalysts is a pivotal reaction in industrial processes, where the metal-substrate interactions often dictate adsorption behaviors and can compromise the selectivity. Here, we employ Sn sites to intermetallize Pd sites for regulating the adsorption behaviors on the Pd-Sn intermetallic surface toward the selective hydrogenation of 4,6-dinitroresorcinol (DNR) to 4,6-diaminoresorcinol (DAR), a key monomer in poly p-phenylene benzobisoxazole (PBO) fiber production. The Pd-Sn intermetallic catalysts were controllably synthesized by in situ growth of Sn(OH)4 on PdMgAl layered double hydroxides (LDHs), followed by a thermally induced structure transformation under hydrogen. By a combination of systematic characterizations and density functional theory calculations, the Sn sites on the intermetallic surfaces are shown to isolate Pd sites and enrich the electron density around the Pd sites. Catalytic tests, kinetics studies, and microkinetics modeling simulations reveal that, as compared with those on the Pd, Pd3Sn, and PdSn2 catalysts, the adsorption of DNR and related intermediates from the hydrogenation is appropriately weakened on the PdSn catalyst due to the well-matched configuration. Such optimized adsorption behaviors promote the activation of hydrogen and desorption of target DAR, resulting in enhanced catalytic activity and selectivity, with DAR selectivity reaching 96.7% at full DNR conversion. These findings highlight a strategy for modulating the strong adsorption of substrates and intermediates on active sites to improve hydrogenation, offering a promising approach for designing high-performance catalysts for selective hydrogenations.