Acta Phys. -Chim. Sin. ›› 2023, Vol. 39 ›› Issue (12): 2212064.doi: 10.3866/PKU.WHXB202212064

• ARTICLE • Previous Articles     Next Articles

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

Zhen Liu1,2,3, Xiangfu Meng4,5, Wanmiao Gu1,3, Jun Zha1,2,3, Nan Yan1,3, Qing You1,3, Nan Xia1,3, Hui Wang4,5,*(), Zhikun Wu1,3,*()   

  1. 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
  • Received:2022-12-31 Accepted:2023-02-14 Published:2023-07-31
  • Contact: Hui Wang, Zhikun Wu E-mail:hw39@hmfl.ac.cn;zkwu@issp.ac.cn
  • Supported by:
    the National Natural Science Foundation of China(21829501);the National Natural Science Foundation of China(21925303);the National Natural Science Foundation of China(22171267);the National Natural Science Foundation of China(22171268);the National Natural Science Foundation of China(21771186);the National Natural Science Foundation of China(21222301);the National Natural Science Foundation of China(21171170);the National Natural Science Foundation of China(21528303);Anhui Provincial Natural Science Foundation(2008085MB31);Anhui Provincial Natural Science Foundation(2108085MB56);CASHIPS Director's Fund(BJPY2019A02);Collaborative Innovation Program of Hefei Science Center, CAS(2020HSC-CIP005);Collaborative Innovation Program of Hefei Science Center, CAS(2022HSC-CIP018)

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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