Poisoning Electrocatalytic CO2 Conversion to CO by Adding a μ4-S Atom on Au60 Nanocluster

IF 9.6 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-05-22 DOI:10.1021/acsmaterialslett.5c0032210.1021/acsmaterialslett.5c00322

Yining Chen, Shuguang Wang, Yan Sun, Xiaoyang Hu, Xiaofeng Lei, Fuling Liu, Afang Dai*, Tiansheng Wei, Zibao Gan* and Xiuwen Zheng*,

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Abstract

Atomically precise gold nanoclusters (APGNCs) have received considerable concern in electrocatalytic carbon dioxide reduction reaction (CO₂RR). The investigation of the CO₂RR of APGNCs with a surface single-atom difference remains challenging. Herein, the successive addition of a surface sulfur atom (μ₄-S) on Au₆₀ was concurrently realized via a modified ligand exchange. The additional μ₄-S makes the outer three kernel gold atoms in situ transform into staple gold atoms without altering other parts, endowing them with optimal model catalysts. Notably, Au₆₀S₆ exhibited high activity and CO selectivity over 95% within the entire test potentials, which decreased with the introduction of a μ₄-S. DFT simulations indicate that the d-band center of the gold active site upshifts toward the Fermi level with the addition of a μ₄-S, which strengthens the adsorption of intermediates, raises the energy barriers for CO desorption. This work provides an unprecedented paradigm for understanding structure–property relationships at the level of a surface single atom.

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在Au60纳米簇上添加μ4-S原子对电催化CO2转化为CO的影响

原子精密金纳米团簇（APGNCs）在电催化二氧化碳还原反应（CO2RR）中受到广泛关注。具有表面单原子差异的APGNCs的CO2RR的研究仍然具有挑战性。本文通过修饰配体交换，实现了Au60表面硫原子（μ4-S）的连续加成。增加的μ4-S使外层的3个核金原子在不改变其他部分的情况下原位转变为短粒金原子，使其具有最佳的模型催化剂。值得注意的是，Au60S6在整个电位范围内具有较高的活性和95%以上的CO选择性，随着μ4-S的引入而降低。DFT模拟表明，加入μ4-S后，金活性位点的d带中心向费米能级上移，加强了中间产物的吸附，提高了CO脱附的能垒。这项工作为理解表面单原子水平上的结构-性质关系提供了一个前所未有的范例。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.