The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being c...The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being challenging.In this work,we developed an acid-induction method and synthesized a Au_(52)(TBBT)_(30)(TBBTH=4-tert-butylbenzenelthiol)nanocluster with the kernel composed of two parts:the amorphous Au_(22)part and the fcc Au_(21)part,which represents the first construction of fcc-amorphous homometal heterojunction with∼1 nm size.Density function theory(DFT)revealed that the HOMO−LUMO majorly distributed in the amorphous part and the HOMO−LUMO gap was dominated by the amorphous part,indicating the redox activity of the amorphous Au_(22)part in contrast to the fcc Au_(21)part,which was experimentally confirmed by differential pulse voltammetry,antioxidation test and anti-Galvanic reaction.But for electro-catalyzing reduction of CO_(2)to CO,the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO_(2)to CO,and the most active sites were assigned to the cosurface sites of amorphous Au_(22)and fcc Au_(21),which is also responsible for the high performance of Au_(52)(TBBT)_(30)relative to the pure fcc-structured Au_(52)(TBBT)_(32)(the highest CO FE:96.7%at−0.67 V vs 73.3%at−0.57 V;CO partial current density at the corresponding potential:−7.3 vs−2.7 mA cm^(−2)).展开更多
基金National Natural Science Foundation of China(Nos.22373082,22471275,21905284,21829501,21925303,22075290,22075291,92475105,U24A20480,22272179,21771186,21528303,21222301,21171170,22403096)Science and Technology Innovation Program of Hunan Province(2023RC1055)+4 种基金Hefei Institute of Physical Science,Chinese Academy of Sciences(BR-E44BGGBR12B)CASHIPS Director’s Fund(BJPY2019A02)Key Program of 13th five-year plan,CASHIPS(KP-2017-16)Collaborative Innovation Program of Hefei Center for Physical Science and Technology(2020HSC-CIP005,2022HSC-CIP018)the State Key Laboratory of Mesoscience and Engineering,Institute of Process Engineering,Chinese Academy of Sciences(MESO-24-A01)for financial support.
文摘The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being challenging.In this work,we developed an acid-induction method and synthesized a Au_(52)(TBBT)_(30)(TBBTH=4-tert-butylbenzenelthiol)nanocluster with the kernel composed of two parts:the amorphous Au_(22)part and the fcc Au_(21)part,which represents the first construction of fcc-amorphous homometal heterojunction with∼1 nm size.Density function theory(DFT)revealed that the HOMO−LUMO majorly distributed in the amorphous part and the HOMO−LUMO gap was dominated by the amorphous part,indicating the redox activity of the amorphous Au_(22)part in contrast to the fcc Au_(21)part,which was experimentally confirmed by differential pulse voltammetry,antioxidation test and anti-Galvanic reaction.But for electro-catalyzing reduction of CO_(2)to CO,the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO_(2)to CO,and the most active sites were assigned to the cosurface sites of amorphous Au_(22)and fcc Au_(21),which is also responsible for the high performance of Au_(52)(TBBT)_(30)relative to the pure fcc-structured Au_(52)(TBBT)_(32)(the highest CO FE:96.7%at−0.67 V vs 73.3%at−0.57 V;CO partial current density at the corresponding potential:−7.3 vs−2.7 mA cm^(−2)).
