文献类型：期刊文献

英文题名：In situ exsolution to fabricate interfacial Ni0/Niδ+ sites for regulating reaction pathways in hydrogenation

作者：Luo, Zuwei[1];Ge, Xiaohu[1];Fang, Di[1];Xu, Xiaofeng[1];Zhang, Dai[1];Cao, Yueqiang[1,2];Duan, Xuezhi[1,2];Li, Wei[1];Zhou, Jinghong[1];Zhou, Xinggui[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Minist Educ, Engn Res Ctr Resource Utilizat Carbon containing W, Shanghai 200237, Peoples R China

年份：2024

卷号：434

外文期刊名：JOURNAL OF CATALYSIS

收录：;EI(收录号：20241916040728);WOS:【SCI-EXPANDED(收录号:WOS:001238613200001)】；

基金：This work was financially supported by the Natural Science Foundation of China (22332003, 22008067, 22178102) , Young Elite Scientists Sponsorship Program by CAST (2023QNRC001) , Shanghai Rising-star Program (23QA1401900) and the Fundamental Research Funds for the Central Universities. We thank the BL11B XAFS beamline of Shanghai Synchrotron Radiation Facility (SSRF) for providing the beamtime.

语种：英文

外文关键词：Selective hydrogenation; Activation behaviors; Interfacial sites; Reaction pathways

摘要：Regulating the selectivity of reaction pathways to desirable products via controlling adsorption/activation behaviors towards reactants is significant for the design of excellent catalysts for selective hydrogenation but remains challenging. Exemplified with dimethyl oxalate (DMO) hydrogenation, we herein propose an in situ exsolution strategy for constructing interfacial Ni0/Ni delta+ sites by using pre-synthesized Ni phyllosilicate as the precursor to control the reaction pathways of selective hydrogenation. Structural characterizations, including in situ spectroscopic and isotopic studies, and theoretical calculations elucidate that the interfacial Ni0/Ni delta+ sites can selectively activate monoester group of DMO via a tilted adsorption configuration and hence boost hydrogen dissociation. With such activation behaviors the reaction pathway is steered to methyl glycolate, other than the pathway to ethylene glycol on the reference active sites where both ester groups are activated and methyl formate is formed via breaking the C-C bond of DMO.