配体尾部基团对金纳米团簇电化学CO2还原过程的影响

doi:10.1016/S1872-2067(25)64908-4

催化学报 ›› 2026, Vol. 81: 195-205.DOI: 10.1016/S1872-2067(25)64908-4

配体尾部基团对金纳米团簇电化学CO₂还原过程的影响

黄立挺, 周业成, 伦永烽, 王琪, 丁朝斌, 宋树芹(), 王毅()

中山大学化学工程与技术学院, 材料科学与工程学院, 广东省低碳化学与节能重点实验室, PCFM实验室, 广东广州 510275

收稿日期:2025-07-30 接受日期:2025-09-08 出版日期:2026-02-18 发布日期:2025-12-26
通讯作者: *电子信箱: wangyi76@mail.syus.edu.cn (王毅),stsssq@mail.sysu.edu.cn (宋树芹).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22478451);国家自然科学基金(22478450);国家自然科学基金(22408408);国家催化重点实验室(2024SKL-A-013);广东省基础与应用基础研究基金(2021A1515010167);广东省基础与应用基础研究基金(2022A1515011196);广州市基础与应用基础研究项目(202201011449);中山大学百人计划研究基金(76110-12230029)

Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO₂ reduction

Liting Huang, Yecheng Zhou, Yongfeng Lun, Qi Wang, Zhaobin Ding, Shuqin Song(), Yi Wang()

Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, PCFM Laboratory, School of Chemical Engineering and Technology, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2025-07-30 Accepted:2025-09-08 Online:2026-02-18 Published:2025-12-26
Contact: *E-mail: wangyi76@mail.sysu.edu.cn (Y. Wang),stsssq@mail.sysu.edu.cn (S. Song).
About author:¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22478451);National Natural Science Foundation of China(22478450);National Natural Science Foundation of China(22408408);National State Key Laboratory of Catalysis(2024SKL-A-013);Guangdong Basic and Applied Basic Research Foundation(2021A1515010167);Guangdong Basic and Applied Basic Research Foundation(2022A1515011196);Guangzhou Basic and Applied Basic Research Project(202201011449);100 Talent Research Foundation of Sun Yat-sen University(76110-12230029)

摘要/Abstract

摘要：

电化学CO₂还原反应(CO₂RR)是将CO₂转化为高附加值化学品的关键技术之一, 对实现碳中和具有重要意义. 金纳米团簇(Au NCs)催化剂因其优异的催化活性及对电催化CO₂RR生成CO的高选择性而广受关注, 而且由于具有明确的分子结构, 成为研究配体效应的理想模型. 本研究聚焦硫醇配体尾部基团结构对电催化CO₂RR性能的影响, 揭示其动态微环境调控机制, 阐明尾部基团通过水溶液中的取向行为影响反应物扩散, 进而调控催化性能, 为配体工程优化催化剂设计提供了理论依据.

本文以原子精确的Au NCs为模型, 创新地聚焦硫醇配体尾部基团结构对电催化CO₂RR性能的影响, 旨在通过单一变量(尾部基团结构)解析其动态微环境调控机制, 为催化剂配体工程设计提供理论指导. 该工作选择2-苯乙硫醇(PET)、1-己硫醇(C6T)和1-十二硫醇(C12T)为保护配体, 通过化学合成法成功制备了三种金核结构相同、配体尾部基团不同的[Au₂₅(SR)₁₈]^‒纳米团簇. 通过电化学测试(线性扫描伏安法、恒电位电解、电化学阻抗谱和Tafel分析等)评估其电催化CO₂RR性能, 同时采用密度泛函理论(DFT)计算和分子动力学(MD)模拟深入探究尾部基团对活性位点电子结构及反应物扩散的影响. 电化学结果表明, [Au₂₅(C12T)₁₈]^‒ NCs在CO路径的活性与选择性方面显著低于[Au₂₅(PET)1₈]^‒和[Au₂₅(C6T)₁₈]^‒, 表明尾部基团结构对CO₂RR反应路径具有显著影响. DFT计算结果显示, 尾部基团对催化剂电子结构的影响可以忽略, 但MD模拟揭示了其在反应界面微环境调控中的关键作用. 具体而言, C12T配体的长链尾部基团易于聚集成束, 产生显著空间位阻并阻碍反应物扩散; 相比之下, PET和C6T配体则呈分散取向, 能够形成均匀的传质通道. 由此说明尾部基团的取向模式(分散或聚集)直接影响了反应物的传输扩散行为, 进而影响了Au NCs电催化CO₂RR的性能.

综上, 本研究为配体保护Au NCs在电催化CO₂RR中的结构-性能关系提供了新颖的理论视角, 利用原子精确的Au NCs模型, 阐明了配体尾部基团通过动态微环境调控CO₂RR性能的机制, 为配体工程优化催化剂设计提供了理论指导, 推动电催化领域结构-性能关系的深入研究, 为可持续能源技术的发展提供了重要参考.

关键词: 金纳米团簇, 电催化二氧化碳还原反应, 精确结构, 配体效应, 界面微环境

Abstract:

The application of thiolate-protected gold nanoclusters (NCs) for the electrochemical CO₂ reduction reaction (CO₂RR) has received widespread attentions. In this work, three types of atomically precise [Au₂₅(SR)₁₈]^‒ NCs protected by 2-phenylethanethiol (PET), 1-hexanethiol (C6T), and 1-dodecanethiol (C12T), respectively, are employed as model catalysts for CO₂RR, where the molecular configuration and length of thiolate ligands are varied. The electrochemical results demonstrate that the [Au₂₅(C12T)₁₈]^‒ NC possesses lower activity and selectivity towards CO formation than [Au₂₅(PET)₁₈]^‒ and [Au₂₅(C6T)₁₈]^‒ NCs. Owing to their identical gold kernels, the differences in electrocatalytic CO₂RR performance of these three Au₂₅ NCs can be fully attributed to their distinctions in tail group structure. Density functional theory (DFT) calculations exclude the possible effects on the electronic structures of the active sites exerted by the distinctions in tail group structure, while molecular dynamics (MD) calculations reveal that different orientation modes of tail groups in aqueous solution affect the diffusion of the reactants to active sites. Overall, this work provides a unique perspective on the structure-property relationships for ligand-protected NCs in electrocatalytic CO₂RR.

Key words: Gold nanoclusters, Electrochemical CO₂ reduction, Precise structure, Ligands effect, Interfacial microenvironment

黄立挺, 周业成, 伦永烽, 王琪, 丁朝斌, 宋树芹, 王毅. 配体尾部基团对金纳米团簇电化学CO₂还原过程的影响[J]. 催化学报, 2026, 81: 195-205.

Liting Huang, Yecheng Zhou, Yongfeng Lun, Qi Wang, Zhaobin Ding, Shuqin Song, Yi Wang. Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2026, 81: 195-205.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64908-4

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图/表 9

Fig. 1. (a) UV-vis spectra of the three Au25 NCs. (b) Negative-mode EIS-MS profiles of [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs. (c) Comparison of the FT-IR spectra of the three Au25 NCs and their respective thiolate ligands (black).

Fig. 2. (a) XPS spectra of [Au25(PET)18]?, [Au25(C6T)18]?, and [Au25(C12T)18]? NCs. (b) Au 4f XPS profiles of the three Au25 NCs. (c) High resolution S 2p XPS profiles of the three Au25 NCs. The experimental data (dots) are shown with envelopes (cyan and purple lines for Au 4f and S 2p, respectively.) and component fitting of Au(0) 4f (green lines), Au(I) 4f (yellow lines), S 2p3/2 (magenta lines), and S 2p1/2 (lavender lines).

Fig. 3. (a) Total current densities at various applied potentials on the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs in a CO2-saturated 0.1 mol L?1 KHCO3 solution. (b) The H2 partial current densities (jH2). (c)The CO partial current densities (jCO) of the three Au25 NCs. (d) The CO Faradaic efficiencies (CO FE). (e) The CO mass activities (MA). (f) The CO turnover frequencies (TOF).

Fig. 4. (a) Nyquist plots from the electrochemical impedance spectra at the respective open circuit potentials of the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs (Inset: the equivalent electric circuit). (b) The Tafel plots of the three Au25 NCs.

Fig. 5. The DFT-optimized and simplified crystal structures of the dethiolated [Au25(PET)(SCH3)16]? NC (a), [Au25(C6T)(SCH3)16]? NC (b), and [Au25(C12T)(SCH3)16]? NC (c) (color codes: yellow, Au; magenta, dethiolated Au site; green, S; gray, C; white, H). (d) Free energy diagrams for the CO formation in CO2RR. (e) H+ reduction to H2 on the three simplified dethiolated Au25 NCs at the potential of ?1.0 V (vs. computational hydrogen electrode, CHE) (* represents the active site).

Fig. 6. The diagrams of Au25 sphere (a), reactive sphere (b), and statistical region (c).

Fig. 7. The time-dependent surface coverage rates of the thiolate ligands on the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta), and [Au25(C12T)18]? (orange) NCs.

Fig. 8. MD simulation snapshots of [Au25(PET)18]? NC (a), [Au25(C6T)18]? NC (b), and [Au25(C12T)18]? NC (c) in aqueous system (the size of H2O molecule is reduced for clarity). Schematic diagrams of the dispersive (d) and concentrative orientation mode (e) of the thiolate ligands in Au25 NCs (the tail groups are simplified as gray curves).

Fig. 9. (a) MSD curves of H2O molecules in the defined statistical regions, of the [Au25(PET)18]? (blue), [Au25(C6T)18]? (magenta) and [Au25(C12T)18]? (orange) NCs systems. (b) The H2O exchange frequencies of the three Au25 NCs systems (the number of H2O molecules exchanged between the defined statistical region and the external environment per fs).

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配体尾部基团对金纳米团簇电化学CO₂还原过程的影响

Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO₂ reduction

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