Interfacial charge effects of supported-metal-cluster heterostructures on azo hydrogenation catalyzation  

作　　者：Zhenhua Gu Jingli Zhang Zijun Zhang Qingxue Mu Liangchong Yu Taolei Sun Lei Shen Guanbin Gao 

机构地区：[1]State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan 430070,China [2]Hubei Key Laboratory of Nanomedicine for Neurodegenerative Diseases,School of Chemistry,Chemical Engineering and Life Science,Wuhan University of Technology,Wuhan 430070,China

出　　处：《Nano Research》2024年第5期3853-3862,共10页纳米研究（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.52273110,21975191,52372271,22173070);the Knowledge Innovation Program of Wuhan Shuguang Project,and the Fundamental Research Funds for the Central Universities(WUT:2023Ⅲ013GX).

摘　　要：The impact of interfacial charge on catalytic performance of supported-metal-cluster(SMC)heterostructures remains unclear,hindering efforts to develop high-performance SMC catalysts.Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters(AuNCs/rGO)for azo hydrogenation.Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol(CSH),amphoteric cysteine(Cys),and electronegative 3-mercaptopropionic-acid(MPA)onto AuNCs/rGO,respectively.All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes.The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO.However,the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO.Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH_(4) action,leading to reduced efficiency and cyclic stability.Conversely,non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration,resulting in better cyclic stability.Protection of amino groups in ligands such as modifying-NH_(3)^(+)group in Cys into imine to form N-isobutyryl-L-cysteine(NIBC)substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system.Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.

关 键 词：interfacial charge effect supported-metal-cluster catalyst azo hydrogenation graphene supported gold nanoclusters 

分 类 号：O64[理学—物理化学]