Adsorption and Hydrogenation Process of p-Chloronitrobenzene on Au_(20)Cluster:a DFT Study  

作　　者：薛继龙 夏盛杰 张连阳 施炜 钱梦丹 倪哲明 

机构地区：[1]College of Chemical Engineering,Zhejiang University of Technology

出　　处：《Chinese Journal of Structural Chemistry》2018年第1期7-14,共8页结构化学（英文）

基　　金：supported by the National Natural Science Foundation of China-No.21503188);the Natural Science Foundation of Zhejiang Province-No.LQ15B030002)

摘　　要：We have systematically investigated the adsorption and hydrogenation process of p-chloronitrobenzene on Au20 cluster using density functional theory-DFT） calculations.The adsorption of two types of all species,vertical adsorption and parallel adsorption,is compared,revealing that former model is more stable than the latter,and all of the species prefer to adsorb at the vertex site.After adsorption,electrons transferred from Au20 cluster to the p-chloronitrobenzene molecule.Almost all hydrogenation processes are exothermic,and the C–Cl bond scissions are considered as the rate-limiting step for both Paths A-p-CNB→p-CAN→AN） and B-p-CNB→NB→AN） with the energy barriers of 2.62 and 2.95 e V,respectively.These suggest that the C–Cl bond scission is not easy to occur on Au20 cluster due to the high energy barrier,especially the path B.The p-chloroaniline is the main hydrogenation product catalyzed by Au20.We have systematically investigated the adsorption and hydrogenation process of p-chloronitrobenzene on Au20 cluster using density functional theory-DFT） calculations.The adsorption of two types of all species,vertical adsorption and parallel adsorption,is compared,revealing that former model is more stable than the latter,and all of the species prefer to adsorb at the vertex site.After adsorption,electrons transferred from Au20 cluster to the p-chloronitrobenzene molecule.Almost all hydrogenation processes are exothermic,and the C–Cl bond scissions are considered as the rate-limiting step for both Paths A-p-CNB→p-CAN→AN） and B-p-CNB→NB→AN） with the energy barriers of 2.62 and 2.95 e V,respectively.These suggest that the C–Cl bond scission is not easy to occur on Au20 cluster due to the high energy barrier,especially the path B.The p-chloroaniline is the main hydrogenation product catalyzed by Au20.

关 键 词：DFT p-chloronitrobenzene Au20 cluster adsorption hydrogenation 

分 类 号：O647.31[理学—物理化学]