Atomically precise copper dopants in metal clusters boost up stability, fluorescence, and photocatalytic activity

Yifei Zhang; Jingjing Zhang; Zhiwen Li; Zhaoxian Qin; Sachil Sharma; Gao Li

doi:10.1038/s42004-023-00817-5

Atomically precise copper dopants in metal clusters boost up stability, fluorescence, and photocatalytic activity

Commun Chem. 2023 Feb 8;6(1):24. doi: 10.1038/s42004-023-00817-5.

Authors

Yifei Zhang^#^{1

2}, Jingjing Zhang^#^{2

3}, Zhiwen Li², Zhaoxian Qin^{4

5}, Sachil Sharma^{2

6}, Gao Li^{7

8}

Affiliations

¹ Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering Shenyang Normal University, Shenyang, 110034, China.
² State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
³ University of Chinese Academy of Sciences, Beijing, 100049, China.
⁴ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. qinzhaoxian@yeah.net.
⁵ University of Chinese Academy of Sciences, Beijing, 100049, China. qinzhaoxian@yeah.net.
⁶ School of Advanced Sciences, Department of Chemistry, Vellore Institute of Technology, Andhra Pradesh (VIT-AP university), Amaravati, Andhra Pradesh, 522237, India.
⁷ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. gaoli@dicp.ac.cn.
⁸ University of Chinese Academy of Sciences, Beijing, 100049, China. gaoli@dicp.ac.cn.

^# Contributed equally.

Abstract

The structurally precise alloy nanoclusters have been emerged as a burgeoning nanomaterial for their unique physical/chemical features. We here report a rod-like nanocluster [Au₁₂Cu₁₃(PPh₃)₁₀I₇](SbF₆)₂ (Au₁₂Cu₁₃), which was generated through a transformation of a [Au₉(PPh₃)₈]³⁺ intermediate in the presence of CuI, unveiled by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry as well as single crystal X-ray diffraction. Au₁₂Cu₁₃ is comprised of two pentagonal bipyramids Au₆Cu units and a pentagonal prism Cu₁₁ unit, where the copper and gold species are presented in +1 and 0 chemical states. The Cu-dopants significantly improved the stability and fluorescence (quantum yield: ~34%, 34-folds of homo-Au₂₅(PPh₃)₁₀Br₇). The high stability of Au₁₂Cu₁₃ is attributed to the high binding energy of iodine ligands, Au-Cu synergistic effects and its 16-electon system as an 8-electron superatom dimer. Finally, the robust Au₁₂Cu₁₃ exhibited high catalytic activity (~92% conversion and ~84% methyl formate-selectivity) and good durability in methanol photo-oxidation.