文献类型：期刊文献

英文题名：Enhanced Interfacial H2 Activation for Nitrostyrene Catalytic Hydrogenation over Rutile Titania-Supported Gold by Coadsorption: A First-Principles Microkinetic Simulation Study

作者：Shao, Zheng-jiang[1,2];Zhang, Lidong[1,2];Liu, Huihui[1,2];Cao, Xiao-Ming[1,2];Hu, P.[1,2,3]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[3]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland

年份：2019

卷号：9

期号：12

起止页码：11288

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20194707710723);WOS:【SCI-EXPANDED(收录号:WOS:000502169900059)】；

基金：The authors gratefully acknowledge the financial support from National Key Research and Development Program of China (2018YFA0208600), NSFC (21673072, 2133303, and 91845111), and Program of Shanghai Subject Chief Scientist (17XD1401400).

语种：英文

外文关键词：Au/TiO2(110); density functional theory; hydrogenation of nitro compounds; microkinetics; heterogeneous catalysis

摘要：Hydrogenation of aromatic nitro compounds is an efficient way to yield aniline, an extremely vital intermediate in many chemical industry fields. However, it is still a great challenge to prepare a catalyst with both high activity and selectivity for this important process when other reducible groups exist at nitroaromatics. Au/TiO2 catalysts could achieve good selectivity for the hydrogenation of nitroarenes with a reducible functional group. However, their activity is still not high. Their fundamental and systematic understandings are still lacking. In this work, the catalytic kinetics of the 4-nitrostyrene (4-NS) hydrogenation system at the binary Au/TiO2 interface is investigated by first-principles heterogeneous site microkinetics simulation. To solve the complex microkinetics model with heterogeneous multiple sites, an efficient hybrid iteration numerical method is proposed and utilized to overcome the stiff problem. Through realistic first-principles calculations and microkinetic analysis, the favorable adsorption configurations and possible catalytic mechanism are determined for 4-NS hydrogenation at the Au/TiO2 interface. It is found that the chemisorption of 4-nitrostyrene could significantly lower the energy barrier of H-2 dissociation at the interface, which could enhance the overall activity of the Au/TiO2 catalyst. It sheds light on a way to promote the activity of selective hydrogenation for metal oxide-supported gold catalysts through modulating the coordination of exposed surface cations.