Cu-In二元金属催化剂上CO2电化学还原

doi:10.1016/S1872-2067(20)63577-X

催化学报 ›› 2020, Vol. 41 ›› Issue (9): 1393-1400.DOI: 10.1016/S1872-2067(20)63577-X

Cu-In二元金属催化剂上CO₂电化学还原

邵加奇^a,b, 王毅^b, 高敦峰^b, 叶克^a,b, 王琪^c, 汪国雄^b

a 哈尔滨工程大学材料科学与化学工程学院超轻材料与表面技术教育部重点实验室, 黑龙江哈尔滨 150001;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 洁净能源国家实验室(筹), 辽宁大连 116023;
c 大连交通大学材料科学与工程学院辽宁省轨道交通关键材料重点实验室, 辽宁大连 116028

收稿日期:2020-01-16 修回日期:2020-02-27 出版日期:2020-09-18 发布日期:2020-08-08
通讯作者: 叶克, 王琪
基金资助:
国家自然科学基金（21802124，91845103）；辽宁省-沈阳材料科学国家研究中心联合研发基金（20180510035）；中国博士后科学基金（2018M630307，2019T120220）；黑龙江省自然科学基金优秀青年项目（YQ2019B002）.

Copper-indium bimetallic catalysts for the selective electrochemical reduction of carbon dioxide

Jiaqi Shao^a,b, Yi Wang^b, Dunfeng Gao^b, Ke Ye^a,b, Qi Wang^c, Guoxiong Wang^b

a Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, Heilongjiang, China;
b State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c Liaoning Key Materials Laboratory for Railway, School of Materials and Engineering, Dalian Jiaotong University, Dalian 116028, Liaoning, China

Received:2020-01-16 Revised:2020-02-27 Online:2020-09-18 Published:2020-08-08
Supported by:
This work was supported by the National Natural Science Foundation of China (21802124 and 91845103), Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science (20180510035), the China Postdoctoral Science Foundation (2018M630307 and 2019T120220) and Excellent Youth Project of Natural Science Foundation of Heilongjiang Province of China (YQ2019B002).

摘要/Abstract

摘要： 石油、天然气和煤等化石能源的转化利用不可避免排放大量的CO₂，造成一系列生态和环境问题.CO₂电化学还原可以在温和反应条件下将CO₂转化为CO或甲酸等，近年来受到研究者广泛关注，但因CO₂具有很稳定的化学结构，CO₂电化学还原要求催化剂具有高的活性，选择性和稳定性.贵金属如金和钯可以有效地将CO₂转化为相应的燃料如CO和甲酸等，但贵金属昂贵的价格限制了其大规模应用，所以迫使人们寻找非贵金属催化剂来替代它们.铟及其合金被应用于CO₂电化学还原生成甲酸，但在低过电位下，这些催化剂的电流密度和选择性都不理想.铜基催化剂也能催化CO₂电化学还原生成甲酸，但在短时间内稳定性较差.因此，需要进一步提高In和Cu催化剂上CO₂电化学还原的电流密度和稳定性.一种可能的解决方案是构建Cu-In双金属催化剂，通过两者的协同作用，有望提升在低过电位下CO₂电化学还原生成甲酸的电流密度和稳定性.
在本工作中，我们通过氢气模板法制备出具有树枝状结构的Cu，然后在其表面均匀电沉积金属In.通过两步电沉积法制备出一种具有树枝状结构的Cu-In二元金属催化剂.控制电沉积In的时长分别为1.5，7.5，15，30和60min.根据SEM及EDX元素分布图谱可知，随着电沉积In时间的增加，In在Cu表面的覆盖率逐渐增高.我们还研究了In的电沉积时间与其电化学活性表面积（ESA）之间的关系.结果表明，In的电沉积时间与其电化学活性表面积成正比，且当电沉积时间达到30min时，电极具有最大的电化学活性表面积.具有树枝状结构的Cu-In-30催化剂ESA数值为8.7cm²，而不具备树枝状结构的In-30催化剂的ESA数值仅为2.4cm².在-0.65V vs.RHE至-1.05V vs.RHE电位窗口中，与其它催化剂相比，Cu-In-30催化剂上CO₂电化学还原生成甲酸的法拉第效率最高可达87.4%.树枝状结构的Cu-In-30催化剂由于具有开放的三维结构，所以能够暴露出更多的活性位，从而提高了催化剂的电化学性能.在-0.85V vs.RHE电位下，甲酸分电流密度可达42.0mA cm^-2，且具有较高的电化学稳定性（12h）.而不具有树枝状结构的In-30催化剂生成甲酸的法拉第效率为57.0%，且甲酸分电流密度为4.6mA cm^-2.

关键词: CO₂电还原, 铜, 铟, 电沉积, 甲酸

Abstract: Copper-indium bimetallic catalysts with a dendritic structure are fabricated by a two-step electrodeposition method using a hydrogen evolution template for the CO₂electroreduction reaction (CO₂RR). The dendritic Cu-In-30 catalyst electrodeposited for 30 min shows the highest specific surface area and exposes the most active sites, resulting in improved CO₂RR activity_. The dendritic Cu-In-30 catalyst exhibits distinctly higher formate partial current density (42.0 mA cm^-2) and Faradaic efficiency (87.4%) than those of the In-30 catalyst without the dendritic structure (the formate partial current density and Faradaic efficiency are 4.6 mA cm^-2and 57.0%, respectively) at -0.85 V vs. reversible hydrogen electrode, ascribed to the increased specific surface area. The Cu-In-30 catalyst can maintain stable performance for 12 h during the CO₂RR. In addition, the intrinsic current density of Cu-In-30 with the dendritic structure (4.8 mA cm^-2) is much higher than that of In-30 without the dendritic structure (2.1 mA cm^-2), indicating that the dendritic structure promotes the CO₂RR, possibly due to additional coordination unsaturated atoms.

Key words: CO₂ electroreduction reaction, Copper, Indium, Electrodeposition, Formate

邵加奇, 王毅, 高敦峰, 叶克, 王琪, 汪国雄. Cu-In二元金属催化剂上CO₂电化学还原[J]. 催化学报, 2020, 41(9): 1393-1400.

Jiaqi Shao, Yi Wang, Dunfeng Gao, Ke Ye, Qi Wang, Guoxiong Wang. Copper-indium bimetallic catalysts for the selective electrochemical reduction of carbon dioxide[J]. Chinese Journal of Catalysis, 2020, 41(9): 1393-1400.

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Cu-In二元金属催化剂上CO₂电化学还原

Copper-indium bimetallic catalysts for the selective electrochemical reduction of carbon dioxide

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