Zuwei Luo , Xiaohu Ge , Di Fang , Xiaofeng Xu , Dai Zhang , Yueqiang Cao , Xuezhi Duan , Wei Li , Jinghong Zhou , Xinggui Zhou
{"title":"原位外溶解法制造界面 Ni0/Niδ+ 位点,用于调节氢化反应途径","authors":"Zuwei Luo , Xiaohu Ge , Di Fang , Xiaofeng Xu , Dai Zhang , Yueqiang Cao , Xuezhi Duan , Wei Li , Jinghong Zhou , Xinggui Zhou","doi":"10.1016/j.jcat.2024.115528","DOIUrl":null,"url":null,"abstract":"<div><p>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 <em>in situ</em> exsolution strategy for constructing interfacial Ni<sup>0</sup>/Ni<sup>δ+</sup> sites by using pre-synthesized Ni phyllosilicate as the precursor to control the reaction pathways of selective hydrogenation. Structural characterizations, including <em>in situ</em> spectroscopic and isotopic studies, and theoretical calculations elucidate that the interfacial Ni<sup>0</sup>/Ni<sup>δ+</sup> 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.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"In situ exsolution to fabricate interfacial Ni0/Niδ+ sites for regulating reaction pathways in hydrogenation\",\"authors\":\"Zuwei Luo , Xiaohu Ge , Di Fang , Xiaofeng Xu , Dai Zhang , Yueqiang Cao , Xuezhi Duan , Wei Li , Jinghong Zhou , Xinggui Zhou\",\"doi\":\"10.1016/j.jcat.2024.115528\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>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 <em>in situ</em> exsolution strategy for constructing interfacial Ni<sup>0</sup>/Ni<sup>δ+</sup> sites by using pre-synthesized Ni phyllosilicate as the precursor to control the reaction pathways of selective hydrogenation. Structural characterizations, including <em>in situ</em> spectroscopic and isotopic studies, and theoretical calculations elucidate that the interfacial Ni<sup>0</sup>/Ni<sup>δ+</sup> 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.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-05-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724002410\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724002410","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
In situ exsolution to fabricate interfacial Ni0/Niδ+ sites for regulating reaction pathways in hydrogenation
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/Niδ+ 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/Niδ+ 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.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.