English

Introducing Novel, Multiple Cd Coordination Modes into Gold Nanoclusters by Combined Doping for Enhancing Electrocatalytic Performance

• Zhen Liu ^{1, 2, 3, †,} ,
• Xiangfu Meng ^{4, 5, †,} ,
• Wanmiao Gu ^{1, 3,} ,
• Jun Zha ^{1, 2, 3,} ,
• Nan Yan ^{1, 3,} ,
• Qing You ^{1, 3,} ,
• Nan Xia ^{1, 3,} ,
• Hui Wang ^{4, 5, ,} ,
• Zhikun Wu ^{1, 3, ,}

• 1.

  Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China

• 2.

  Science Island Branch, Graduate School of University of Science and Technology of China, Hefei 230026, China

• 3.

  Institute of Physical Science and Information Technology, Anhui University, Hefei 230601, China

• 4.

  High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China

• 5.

  Hefei National Laboratory for Physical Science at Microscale, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China

• ^†These authors contributed equally to this work.

Corresponding author: Hui Wang, hw39@hmfl.ac.cn Zhikun Wu, zkwu@issp.ac.cn

• Received Date: 31 December 2022
  Accepted Date: 14 February 2023
  Revised Date: 11 February 2023
  Available Online: 15 December 2023
• Fund Project:

Abstract: In recent years, gold nanoclusters have been widely used in catalysis, and alloying has become one of the most important methods for improving the catalytic performance of gold nanoclusters. As for the electrocatalytic reduction of CO₂ (CO₂RR), although many gold nanoclusters show fairly good Faraday efficiencies through Cd-doping, they still exhibit low current density. Furthermore, as an increasing number of Au-Cd alloy nanoclusters are reported, there is a growing interest in understanding the correlation between Cd coordination and catalysis performance. In most cases, Cd atoms are typically doped in the outer staples and connect with Au atoms through S coordinations. Are there any other unreported Cd coordination modes? Can novel or numerous Cd coordination modes be introduced into gold nanoclusters to increase the current density in the CO₂RR? This study investigates these questions.Inspired by our previous work on surface sulfur doping, we employed a combined doping (S + Cd doping) strategy, developed a two-step synthesis method, and successfully synthesized a novel Au-Cd nanocluster—Au₄₁Cd₆S₂(SCH₂Ph)₃₃. Precise formula and structure were determined by electrospray ionization mass spectrometry (ESI-MS), thermalgravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and single-crystal X-ray crystallography (SCXC). SCXC shows that the nanocluster contains a biicosahedral Au₂₃ kernel, and all the Cd atoms are doped in the outer staples, providing a variety of coordination environments for Cd atoms. In addition to two common Au₃(SR)₄ trimers in the outer staples, two unusual Au₅Cd₂(SR)₉S long staples were discovered cross-covering the top of the kernel, and a (S-Au-S)₂(CdS-S-CdS) tetramer staple with two Cd atoms directly linked through S was also discovered for the first time. This alloy cluster shows robust stability in both high-temperature and oxidation environments. Compared with the "homo-kernel-hetero-staples" nanocluster Au₃₈(SCH₂Ph)₂₄, Au₄₁Cd₆S₂(SCH₂Ph)₃₃ exhibits distinct UV-Vis/NIR absorption and differential pulse voltammetry (DPV) results, indicating that the differences in the outer staples have a significant effect on the optical and electronic properties of gold nanoclusters. When used as an electrocatalyst, the Au₄₁Cd₆S₂(SCH₂Ph)₃₃ exhibits a higher Faradaic efficiency for the CO₂RR (99.3% at −0.7 V) and a higher CO partial current density (120 mA∙cm⁻² at −0.9 V) than Au₃₈(SCH₂Ph)₂₄, providing an ideal platform for investigating the roles of different Cd coordination modes in outer staples on CO₂RR. DFT calculations interpret the experimental finding that Cd doping improves the catalytic performance and reveal that the Cd-Cd site is the most active site and the Au-Cd site furthest away from the kernel is the best-performing catalytic site given the consideration of both selectivity and activity.This work introduces a novel strategy to enhance the catalytic performance of gold nanoclusters, having important implications for future research on the syntheses and structural properties of metal nanoclusters, and is expected to inspire more work in related areas.

Key words:
• Metal Nanocluster
•  /  Combined doping
•  /  Cd-coordination mode
•  /  Structure-property correlation
•  /  Electrocatalytic reduction of CO₂

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