Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18](2-) (M = Pd, Pt) Clusters.
Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18](2-) (M = Pd, Pt) Clusters.
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DOI：
10.1021/jacs.5b07186
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发表时间：
2015-09
影响因子：
15
通讯作者：
Juanzhu Yan;Haifeng Su;Huayan Yang;Sami Malola;Shui-Lian Lin;H. Häkkinen;N. Zheng
中科院分区：
文献类型：
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作者：
Juanzhu Yan;Haifeng Su;Huayan Yang;Sami Malola;Shui-Lian Lin;H. Häkkinen;N. Zheng
通过引入钯或铂原子，首次成功制备了硫醇化的富银25原子纳米团簇，并对其结构进行了表征。在[PdAg 24（SR）18]（2-）或[PtAg 24（SR）18]（2-）的组成下，所获得的25个金属原子的纳米团簇具有与广泛研究的Au 25（SR）18类似的金属骨架结构。在这两个簇中，M @ Ag 12（M = Pd，Pt）核心被六个扭曲的二聚体-RS-Ag-SR-Ag-SR-单元封端。然而，银-硫醇盐覆盖层产生与Au 25（SR）18不同的几何手性。通过测量吸收光谱和从头算分析研究了掺杂对电子结构的影响。这项工作表明，通过过渡金属掺杂来调节电子结构有望提供有效的手段来操纵硫醇化贵金属纳米团簇的电子、光学、化学和催化性质。
With the incorporation of Pd or Pt atoms, thiolated Ag-rich 25-metal-atom nanoclusters were successfully prepared and structurally characterized for the first time. With a composition of [PdAg24(SR)18](2-) or [PtAg24(SR)18](2-), the obtained 25-metal-atom nanoclusters have a metal framework structure similar to that of widely investigated Au25(SR)18. In both clusters, a M@Ag12 (M = Pd, Pt) core is capped by six distorted dimeric -RS-Ag-SR-Ag-SR- units. However, the silver-thiolate overlayer gives rise to a geometric chirality at variance to Au25(SR)18. The effect of doping on the electronic structure was studied through measured optical absorption spectra and ab initio analysis. This work demonstrates that modulating electronic structures by transition-metal doping is expected to provide effective means to manipulate electronic, optical, chemical, and catalytic properties of thiolated noble metal nanoclusters.