Surface Ligand Evolution:Sulfur-Directed Covalent Bonding of PPh_(3) on Pd_(4)S with Improved Semi-hydrogenation of Terminal Alkynes  

作　　者：Wentong Jing Shiguang Mo Weijie Zhang Wenting Zhou Kunlong Liu Jie Wei Ruixuan Qin Nanfeng Zheng 

机构地区：[1]New Cornerstone Science Laboratory,State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,and National&Local Joint Engineering Research Center of Preparation Technology of Nanomaterials,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]China Resources Cement Technology R&D(Guangxi)Co Ltd.,Nanning 530008,China [3]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen 361102,China

出　　处：《Precision Chemistry》2024年第5期200-207,共8页精准化学（英文）

基　　金：National Natural Science Foundation of China(grant no.92261207,and NSFC Center for Single-Atom Catalysis under grant no.22388102);New Cornerstone Science Foundation.R.Q.acknowledges support from National Key R&D Program of China(2022YFA1504500);Young Scientists Fund of the National Natural Science Foundation of China(22202164);Natural Science Foundation of Fujian Province(2023J05006);Fundamental Research Funds for the Central Universities(20720230002).

摘　　要：Surface modification of metallic nanocatalysts with organic ligands has emerged as an effective strategy to enhance catalytic selectivity,although offten at the expense of catalytic activity.In this study,we demonstrate a compelling approach by surface modifying Pd2S nanocrystals with PPhz ligands,resulting in a catalyst with excellent catalytic activity and durable selectivity for the semi-hydrogenation of terminal alkynes.Experimental and theoretical investigations reveal that the presence of S sites on the Pd surface directs PPh_(3) ligands to preferentially form covalent bonds with S,creating distinctive surface S=PPh_(3) motifs.This configuration induces a partial positive charge on Pd,facilitating hydrogen transfer and thus promoting catalytic activity.Furthermore,the covalent bond between the ligand and catalyst surface forms a robust network,ensuring ligand stability and increasing the hydrogenation energy barrier of olefins.Consequently,the Pd_(4)S@PPhz catalyst exhibits an improved catalytic selectivity with durability in terminal alkyne semi-hydrogenation.This study introduces an effective strategy for designing selective hydrogenation catalysts with an enhanced performance.

关 键 词：Pd nanocatalysts surface modification selective hydrogenation catalytic stability alkyne semi-hydrogenation 

分 类 号：O64[理学—物理化学]