Thiol-stabilized atomically precise, superatomic silver nanoparticles for catalysing cycloisomerization of alkynyl amines  

作　　者：Juanzhu Yan Jun Zhang Xumao Chen Sami Malola Bo Zhou Elli Selenius Xiaomin Zhang Peng Yuan Guocheng Deng Kunlong Liu Haifeng Su Boon K.Teo Hannu Hakkinen Lansun Zheng Nanfeng Zheng 

机构地区：[1]State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials,and Engineering Research Center for Nano-Preparation Technology of Fujian Province,College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China [2]School of Materials and Chemical Engineering, Anhui Jianzhu University,Hefei 230601,China [3]Departments of Physics and Chemistry, Nanoscience Center, University of Jyvaskyla,FI-40014 Jyvaskyla,Finland

出　　处：《National Science Review》2018年第5期694-702,共9页国家科学评论（英文版）

基　　金：the National Key R&D Program of China(2017YFA0207302);the National Natural Science Foundation of China(21731005,21420102001,21333008,21390390);The financial support from iChEM,Xiamen University(to B.T.);from National Innovation and Intelligence Introduction Base Program(to H.H.);the University of Jyvskylwas supported by the Academy of Finland(266492and Academy Professorship to H.H.)

摘　　要：Both the electronic and surface structures of metal nanomaterials play critical roles in determining their chemical properties. However, the non-molecular nature of conventional nanoparticles makes it extremely challenging to understand the molecular mechanism behind many of their unique electronic and surface properties. In this work, we report the synthesis, molecular and electronic structures of an atomically precise nanoparticle, [Ag206 L72]~q(L = thiolate, halide; q = charge). With a four-shell Ag7@Ag32@Ag77@Ag90 Ino-decahedral structure having a nearly perfect D_(5h) symmetry, the metal core of the nanoparticle is co-stabilized by 68 thiolate and 4 halide ligands. Both electrochemistry and plasmonic absorption reveal the metallic nature of the nanoparticles, which is explained by density functional theory calculations.Electronically, the nanoparticle can be considered as a superatom, just short of a major electron shell closing of 138 electrons(q = –4). More importantly, many of ligands capping on the nanoparticle are labile due to their low-coordination modes, leading to high surface reactivity for catalysing the synthesis of indoles from 2-ethynylaniline derivatives. The results exemplify the power of the atomic-precision nanocluster approach to catalysis in probing reaction mechanisms and in revealing the interplay of heterogeneous reactivities,electronic and surface structural dynamics, thereby providing ways for optimization.Both the electronic and surface structures of metal nanomaterials play critical roles in determining their chemical properties. However, the non-molecular nature of conventional nanoparticles makes it extremely challenging to understand the molecular mechanism behind many of their unique electronic and surface properties. In this work, we report the synthesis, molecular and electronic structures of an atomically precise nanoparticle, [Ag206 L72]~q(L = thiolate, halide; q = charge). With a four-shell Ag7@Ag32@Ag77@Ag90 Ino-decahedral structure having a nearly perfect D_(5h) symmetry, the metal core of the nanoparticle is co-stabilized by 68 thiolate and 4 halide ligands. Both electrochemistry and plasmonic absorption reveal the metallic nature of the nanoparticles, which is explained by density functional theory calculations.Electronically, the nanoparticle can be considered as a superatom, just short of a major electron shell closing of 138 electrons(q = –4). More importantly, many of ligands capping on the nanoparticle are labile due to their low-coordination modes, leading to high surface reactivity for catalysing the synthesis of indoles from 2-ethynylaniline derivatives. The results exemplify the power of the atomic-precision nanocluster approach to catalysis in probing reaction mechanisms and in revealing the interplay of heterogeneous reactivities,electronic and surface structural dynamics, thereby providing ways for optimization.

关 键 词：METAL nanoclusters atomically-precise nanoparticles NOBEL METAL superatom NANOCATALYSIS 

分 类 号：N[自然科学总论]