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Research Article

Tailoring optical and photocatalytic properties by single-Ag-atom exchange in Au13Ag12(PPh3)10Cl8 nanoclusters

Zhaoxian Qin1,4,§, Song Hu3,4,§, Wenhua Han2, Zhiwen Li1,4, Wen Wu Xu2( ), Jingjing Zhang1,4, Gao Li1,4( )
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Department of Physics, School of Physical Science and Technology, Ningbo University, Ningbo 315211, China
CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China

§ Zhaoxian Qin and Song Hu contributed equally to this work.

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Graphical Abstract

We here develop a highly controllable strategy for exchanging a single Ag atom into the central gold site of Au13Ag12(PPh3)10Cl8 (Ph = phenyl) nanoclusters to tailor their electronic properties on the enhancement of fluorescence and catalytic activity in the photocatalytic oxidation.

Abstract

Precise mono-doping of metal atom into metal particles at a specific particle position (e.g., the central site) in a highly controllable manner is still a challenge. In this work, we develop a highly controllable strategy for exchanging a single Ag atom into the central gold site of Au13Ag12(PPh3)10Cl8 (Ph = phenyl) nanoclusters. Interestingly, a “pigeon-pair” cluster of {[Au13Ag12(PPh3)10Cl8]·[Au12Ag13(PPh3)10Cl8]}2+ is obtained and confirmed by electrospray ionization mass spectrometry (ESI-MS), thermogravimetric analysis (TGA) and single crystal X-ray diffraction (SCXRD) analysis. The experimental results and density functional theory (DFT) calculations suggest that the single-metal-atom exchanging from [Au13Ag12(PPh3)10Cl8]+ to [Au12Ag13(PPh3)10Cl8]+ occurs at the central position through the side entry of the μ3-bridging Cl atoms. Finally, the effects on the electronic structure and properties caused by the single-atom exchange at the central site are shown by the enhancement of fluorescence and catalytic activity in the photocatalytic oxidation of ethanol.

Keywords

single atom exchangenanoclustersphotoluminescence enhancementphotocatalyst of ethanolalloy clusters

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Nano Research
Volume 15 Issue 4,
April 2022
Pages 2971-2976
DOI: 10.1007/s12274-021-3928-4
Cite this article:
Qin Z, Hu S, Han W, et al. Tailoring optical and photocatalytic properties by single-Ag-atom exchange in Au13Ag12(PPh3)10Cl8 nanoclusters. Nano Research, 2022, 15(4): 2971-2976. https://doi.org/10.1007/s12274-021-3928-4
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Received: 18 August 2021
Revised: 17 September 2021
Accepted: 30 September 2021
Published: 04 November 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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