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Precise control of alloying sites of bimetallic nanoclusters via surface motif exchange reaction

Author

Listed:
  • Qiaofeng Yao

    (National University of Singapore)

  • Yan Feng

    (National University of Singapore
    Institute of Process Engineering, Chinese Academy of Sciences)

  • Victor Fung

    (University of California)

  • Yong Yu

    (National University of Singapore)

  • De-en Jiang

    (University of California)

  • Jun Yang

    (Institute of Process Engineering, Chinese Academy of Sciences)

  • Jianping Xie

    (National University of Singapore)

Abstract

Precise control of alloying sites has long been a challenging pursuit, yet little has been achieved for the atomic-level manipulation of metallic nanomaterials. Here we describe utilization of a surface motif exchange (SME) reaction to selectively replace the surface motifs of parent [Ag44(SR)30]4− (SR = thiolate) nanoparticles (NPs), leading to bimetallic NPs with well-defined molecular formula and atomically-controlled alloying sites in protecting shell. A systematic mass (and tandem mass) spectrometry analysis suggests that the SME reaction is an atomically precise displacement of SR–Ag(I)–SR-protecting modules of Ag NPs by the incoming SR–Au(I)–SR modules, giving rise to a core-shell [Ag32@Au12(SR)30]4−. Theoretical calculation suggests that the thermodynamically less favorable core-shell Ag@Au nanostructure is kinetically stabilized by the intermediate Ag20 shell, preventing inward diffusion of the surface Au atoms. The delicate SME reaction opens a door to precisely control the alloying sites in the protecting shell of bimetallic NPs with broad utility.

Suggested Citation

  • Qiaofeng Yao & Yan Feng & Victor Fung & Yong Yu & De-en Jiang & Jun Yang & Jianping Xie, 2017. "Precise control of alloying sites of bimetallic nanoclusters via surface motif exchange reaction," Nature Communications, Nature, vol. 8(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-01736-5
    DOI: 10.1038/s41467-017-01736-5
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    Cited by:

    1. Zhi Wang & Yan-Jie Zhu & Ying-Zhou Li & Gui-Lin Zhuang & Ke-Peng Song & Zhi-Yong Gao & Jian-Min Dou & Mohamedally Kurmoo & Chen-Ho Tung & Di Sun, 2022. "Nuclearity enlargement from [PW9O34@Ag51] to [(PW9O34)2@Ag72] and 2D and 3D network formation driven by bipyridines," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Xiao-Li Pei & Pei Zhao & Hitoshi Ube & Zhen Lei & Masahiro Ehara & Mitsuhiko Shionoya, 2024. "Single-gold etching at the hypercarbon atom of C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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