Heterointerface of all-alkynyl-protected Au_(28) nanoclusters anchored on NiFe-LDHs boosts oxygen evolution reaction:a case to unravel ligand effect  

作　　者：Quan-Li Shen Long-Yun Shen Le-Yi Chen Lu-Bing Qin Yong-Gang Liu Nicholas M.Bedford Francesco Ciucci Zheng-Hua Tang 

机构地区：[1]School of Environment and Energy,Guangzhou Higher Education Mega Centre,New Energy Research Institute,South China University of Technology,Guangzhou 510006,China [2]Division of Emerging Interdisciplinary Areas,The Hong Kong University of Science and Technology,Hong Kong 999077,China [3]Department of Mechanical and Aerospace Engineering,The Hong Kong University of Science and Technology,Hong Kong 999077,China [4]School of Chemical Engineering,University of New South Wales Sydney,Sydney,NSW2052,Australia [5]HKUST Shenzhen-Hong Kong Collaborative Innovation Research Institute,Shenzhen 518048,China [6]Energy Institute,The Hong Kong University of Science and Technology,Hong Kong 999077,China

出　　处：《Rare Metals》2023年第12期4029-4038,共10页稀有金属（英文版）

基　　金：financially supported by Guangdong Natural Science Funds (No.2022A1515011840);the Research Grant Council of Hong Kong for support through the projects (Nos.16201820 and 16206019);the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone (No.HZQB-KCZYB-2020083)。

摘　　要：Ultrasmall Au nanoclusters have been proven to effectively enhance the catalytic performance of NiFe layered double hydroxides(NiFe-LDHs)toward oxygen evolution reaction(OER),yet the surface ligand effect of the Au nanoclusters still remains elusive.Herein,a systematic study is reported to examine the OER performance of NiFe-LDHs supported atom-precise all alkynyl-protected[Au_(28)(~tBuC≡C)17]~-nanoclusters(Au_(28)-Alkynyl in short)and thiolate-protected Au_(28)(TBBT)_(20)(TBBT=4-tert-butylbenzene thiol)counterp arts(Au_(28)-Thiolate in short).The Au_(28)-Alkynyl cluster has characteristic absorbance feature,and its composition is verified by mass spectrometry.It possesses a drastically different structure from the reported mixed ligand protected Au_(28)nanoclusters.Interestingly,the NiFe-LDHs loaded with Au_(28)-Alkynyl exhibited a superior OER performance than the sample loaded with Au28-Thiolate under the same conditions,evidenced by a smaller overpotential of 205 mV at the current density of 10 mA·cm^(-2)and a lower Tafel slope value of 41.0 mV·dec^(-1)in 1 mol·L^(-1)KOH.Such excellent performance is attributed to the interfaces created between the NiFe-LDHs and the Au nanoclusters,as density functional theory calculations reveal that more significant charge transfer occurs in Au_(28)-Alkynyl/NiFeLDHs catalyst,and more importantly,the energy barrier of the potential-determining step in the OER process for Au28-Alkynyl/NiFe-LDHs is much lower than that of Au28-Thiolate/NiFe-LDHs hence favors the electrocatalytic reaction.

关 键 词：NiFe layered double hydroxides Au_(28)nanoclusters Alkynyl ligand Oxygen evolution reaction Density functional theory calculations 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O643.36[理学—物理化学]