一个金属纳米团簇压缩结构的构筑与转化  

A compressed structure construction and transformation in metal nanoclusters

作　　者：查珺 范文涛 夏楠 尤青 闫楠 廖玲文 李进 邓海腾 伍志鲲 Jun Zha;Wentao Fan;Nan Xia;Qing You;Nan Yan;Lingwen Liao;Jin Li;Haiteng Deng;Zhikun Wu(Key Laboratory of Materials Physics,Anhui Key Laboratory of Nanomaterials and Nanotechnology,CAS Center for Excellence in Nanoscience,Institute of Solid State Physics,HFIPS,Chinese Academy of Sciences,Hefei 230031,China;University of Science and Technology of China,Hefei 230026,China;Institute of Physical Science and Information Technology,Anhui University,Hefei 230601,China;Tsinghua University-Peking University Joint Center for Life Sciences,School of Life Sciences,Tsinghua University,Beijing 100084,China;MOE Key Laboratory of Bioinformatics,School of Life Sciences,Tsinghua University,Beijing 100084,China)

机构地区：[1]Key Laboratory of Materials Physics,Anhui Key Laboratory of Nanomaterials and Nanotechnology,CAS Center for Excellence in Nanoscience,Institute of Solid State Physics,HFIPS,Chinese Academy of Sciences,Hefei 230031,China [2]University of Science and Technology of China,Hefei 230026,China [3]Institute of Physical Science and Information Technology,Anhui University,Hefei 230601,China [4]Tsinghua University-Peking University Joint Center for Life Sciences,School of Life Sciences,Tsinghua University,Beijing 100084,China [5]MOE Key Laboratory of Bioinformatics,School of Life Sciences,Tsinghua University,Beijing 100084,China

出　　处：《Science China Materials》2023年第8期3367-3372,共6页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22171267,21829501,21925303,21701179,21771186,21501181,21222301,and 21528303);Anhui Provincial Natural Science Foundation(2008085MB31 and 2108085MB56);Hefei Institutes of Physical Science,Chinese Academy of Sciences(CASHIPS)Director’s Fund(BJPY2019A02);China Postdoctoral Science Foundation(Y94G4E356B);the Key Program of the 13th Five Year Plan,CASHIPS(KP-2017-16);the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2020HSC-CIP005 and 2022HSC-CIP018);the CAS/SAFEA International Partnership Program for Creative Research Teams.

摘　　要：尽管已开展了不少金属纳米团簇方面的研究,但表面配体对结构的影响还没有被很好地理解.例如,表面配体的挤压可能对团簇结构产生影响,这一点没有被广泛意识到.我们通过使用具有不同挤压作用的配体来构筑和转化一个新的团簇,对此进行了证实:我们将前期合成中使用的配体3-甲氧基苯硫酚替换成位阻更大(挤压作用更强)的4-叔丁基苯硫酚,获得了比原来(AgCu)_(50)团簇更为压缩的(AgCu)_(27)结构(原子层间距最短达1.21Å).在此基础上,通过与位阻较小的碘离子的交换反应,将(AgCu)_(27)转化为压缩程度相对较轻的Ag_(55)Cu_(8)I_(12)面心立方结构(平均层间距为2.03Å).值得一提的是,引入的碘离子交换转换反应未曾在金属纳米团簇领域报道过,本文证明该转换方法具有一定的普适性,因而不仅为金属纳米团簇的合成(尤其是相对起始团簇尺寸显著增大的团簇的合成),而且为I−的传感提供了一种新的策略.进一步通过理论计算解释了(AgCu)_(27)团簇对卤素离子中I−具有选择性的原因.总之,该工作引入了一种新颖且通用的纳米团簇合成或离子传感策略,为利用配体的物理作用提供了新的视角,并加深了对纳米团簇内核和表面无机配体相互作用的理解.Metal nanoclusters have emerged as a new type of star materials partly owing to their tunable and well-defined compositions and structures with atomic precision[1–4].Especially the tunability provides good opportunities for the property improvement aiming at practical applications[5–10].Ligand(including organic or inorganic)engineering has been realized as an efficient strategy to tune the structures and properties,and the metal–ligand coordination is always a consideration for the ligand engineering[11–16].However.

关 键 词：压缩程度 交换反应 物理作用 卤素离子 碘离子 挤压作用 苯硫酚 纳米团簇 

分 类 号：O641.1[理学—物理化学] TB383.1[理学—化学]