Au<sub>24</sub>和Au<sub>25</sub>纳米团簇对二氧化碳电化学还原反应催化活性的分析

引用本文: 刘凯梵, 李宗军, 陈卫. Au₂₄和Au₂₅纳米团簇对二氧化碳电化学还原反应催化活性的分析[J]. 分析化学, 2022, 50(4): 593-601. doi: 10.19756/j.issn.0253-3820.221092 shu

Citation: LIU Kai-fan, LI Zong-jun, CHEN Wei. Electrocatalytic Activities of Au₂₄ and Au₂₅ Nanoclusters for Carbon Dioxide Reduction Reaction[J]. Chinese Journal of Analytical Chemistry, 2022, 50(4): 593-601. doi: 10.19756/j.issn.0253-3820.221092 shu

Au₂₄和Au₂₅纳米团簇对二氧化碳电化学还原反应催化活性的分析

1.
中国科学院长春应用化学研究所，电分析化学国家重点实验室，长春 130022;2 中国科学技术大学，合肥 230026）

通讯作者: 陈卫,E-mail:weichen@ciac.ac.cn

基金项目:
国家自然科学基金项目(No.21773224)资助

科技部重点研发计划项目(No.2020YFB1506001)

摘要: 通过电化学催化过程将二氧化碳(CO₂)还原为有用的燃料和化学品是目前降低CO₂排放量以及高效利用CO₂的主要方式之一。金纳米团簇(Au NCs)因其结构明确、原子级尺寸精确和高表面活性而被认为是CO₂电化学还原反应(CO₂RR)的良好催化材料和模型催化剂。本研究可控合成了两种金纳米团簇Au₂₄ NCs和Au₂₅ NCs,并研究了其对CO₂RR的催化活性。通过将Au₂₄ NCs和Au₂₅ NCs负载在碳基底上,制备的Au₂₄ NCs/C和Au₂₅ NCs/C催化剂表现出了优异的CO₂RR活性和高的CO转化率。其中,Au₂₄ NCs/C在–0.58 V达到77.5%的CO法拉第效率,Au₂₅ NCs/C在–0.68 V达到68.9%的CO法拉第效率,即Au₂₄ NCs/C比Au₂₅ NCs/C的CO法拉第效率提高了8.6%。同时,相比于Au₂₅ NCs/C,在Au₂₄ NCs/C上CO达最高法拉第效率的电位正移100 mV,表明Au₂₄ NCs/C对CO₂RR催化活性更高。Au₂₄ NCs和Au₂₅ NCs不同的CO₂RR催化活性可归因于二者不同的配位结构。Au₂₄ NCs比Au₂₅ NCs缺少一个中心原子,因而其外围配体在电化学过程中可能更易脱落,使得暴露的Au活性位点增多,导致Au₂₄ NCs/C比Au₂₅ NCs/C具有更优异的CO₂RR催化性能。另外,Au₂₄ NCs和Au₂₅ NCs不同的结构会影响团簇的电子分布和表面原子活性,从而影响其催化活性。本研究为设计高性能、高选择性的CO₂RR催化剂提供了参考。

关键词:

English

Electrocatalytic Activities of Au₂₄ and Au₂₅ Nanoclusters for Carbon Dioxide Reduction Reaction

1.
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;2 University of Science and Technology of China, Hefei 230026, China

Corresponding author: CHEN Wei, weichen@ciac.ac.cn

Received Date: 22 February 2022
Revised Date: 22 March 2022
Fund Project:
the National Natural Science Foundation of China(No. 21773224)

Supported by the National Key Research and Development Plan(No. 2020YFB1506001)

Abstract: Reduction of CO₂ into useful fuels and chemicals through electrochemical catalytic processes is currently the most promising way to address CO₂ emissions and utilize CO₂.Herein, we report a method to use atomically well-defined gold nanoclusters Au₂₄ NCs and Au₂₅ NCs as catalytically active sites for electrochemical carbon dioxide electroreduction reaction (CO₂RR) by supporting the as-prepared Au₂₄ NCs and Au₂₅ NCs on carbon substrates.The electrochemical results show that Au₂₄ NCs/C achieves the highest CO Faradaic efficiency of 77.5%at-0.58 V, and Au₂₅ NCs/C achieves the highest CO Faradaic efficiency of 68.9% at-0.68 V.By comparison, it can be found that the highest CO Faradaic efficiency obtained on Au₂₄ NCs/C is 8.6% higher than that on Au₂₅ NCs/C.Meanwhile, compared to Au₂₅ NCs/C, the potential for the highest CO Faradaic efficiency has a positive shift of 100 mV on Au₂₄ NCs/C.These data indicate that Au₂₄ NCs/C has better catalytic activity than Au₂₅ NCs/C for CO₂RR, which may be attributed to the different coordination structures of the two gold clusters.Compared with Au₂₅ NCs/C, Au₂₄ NCs/C lacks a central atom, and therefore its peripheral ligands may be more easily to drop off from the cluster surface, resulting in more exposed Au active sites for CO₂RR.This study reveals the structure effect of metal clusters on their electrocatalytic properties and is helpful for the design of high-performance and highly selective CO₂RR catalysts.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Au₂₄和Au₂₅纳米团簇对二氧化碳电化学还原反应催化活性的分析

通讯作者: 陈卫,E-mail:weichen@ciac.ac.cn

English

Electrocatalytic Activities of Au₂₄ and Au₂₅ Nanoclusters for Carbon Dioxide Reduction Reaction

Corresponding author: CHEN Wei, weichen@ciac.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Au24和Au25纳米团簇对二氧化碳电化学还原反应催化活性的分析

通讯作者: 陈卫,E-mail:weichen@ciac.ac.cn

English

Electrocatalytic Activities of Au24 and Au25 Nanoclusters for Carbon Dioxide Reduction Reaction

Corresponding author: CHEN Wei, weichen@ciac.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Au₂₄和Au₂₅纳米团簇对二氧化碳电化学还原反应催化活性的分析

Electrocatalytic Activities of Au₂₄ and Au₂₅ Nanoclusters for Carbon Dioxide Reduction Reaction

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