Research progress on copper-based catalysts for electrochemical reduction of carbon dioxide to formic acid

doi:10.16085/j.issn.1000-6613.2023-0843

Abstract

Abstract:

The electrochemical reduction of carbon dioxide (ECO₂RR) presents a significant value for carbon neutrality by preparing high-energy chemicals or fuels from renewable energy. Particularly, ECO₂RR using copper-based catalysts, with their advantages of low cost and excellent catalytic activity, has emerged as the most promising strategy. In this paper, the research progress of copper-based catalysts in the preparation of formic acid in recent years is comprehensively summarized. The adjusting strategies of ECO₂RR to formic acid include morphology, surface valence, alloying, crystal plane effect, vacancy and carbon carrier. The effects of the number of active sites and the formation of key intermediate *OCHO on the selectivity of formic acid products are discussed. Finally, the challenges faced in this field and the prospects from the perspectives of in-situ characterization, scientific calculation and reaction condition optimization are summarized.

Key words: electrocatalysis, carbon dioxide reduction, Cu-based catalyst, formic acid

摘要：

电化学二氧化碳还原（ECO₂RR）通过可再生能源制备高能量化学品或燃料对碳中和具有巨大价值。尤其是以铜基催化剂进行的ECO₂RR，其成本优势和卓越的催化活性使其成为最有前景的策略。在ECO₂RR的各种产物中，甲酸作为优秀的储氢材料和内燃机燃料展现出工业化生产潜力。本文针对近年来过渡金属族的铜基催化剂在制备甲酸的研究进展进行了全面的总结，从ECO₂RR制甲酸机理出发，综述了铜基催化剂在ECO₂RR制甲酸领域取得的重要研究进展，其中以典型催化剂为例分析ECO₂RR生成甲酸的策略，包括形貌结构、表面价态、合金化、晶面效应、空位和碳载体等，重点讨论了活性位点数量以及关键中间体*OCHO的形成对甲酸产物选择性的影响，最后总结了该领域面临的挑战以及从原位表征、科学计算和反应条件等角度的展望。

关键词: 电催化, 二氧化碳还原, 铜基催化剂, 甲酸

CLC Number:

O646

CHEN Fuqiang, ZHONG Zhaoping, QI Renzhi. Research progress on copper-based catalysts for electrochemical reduction of carbon dioxide to formic acid[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3051-3060.

陈富强, 仲兆平, 戚仁志. 铜基催化剂电还原二氧化碳为甲酸研究进展[J]. 化工进展, 2024, 43(6): 3051-3060.

Figures/Tables 11

催化剂	策略	$F E H C O O -$ /%	电流密度/mA·cm^-2	参考文献
多孔树枝Cu	形貌调整	87	6.5	[21]
三维核壳Cu@Sn	形貌调整	100	16.52	[22]
中空纤维Cu	形貌调整	77.1	34.7	[23]
Pd₅Cu₁	合金化	64	—	[24]
CdCu@Cu	合金化	70.5	30.5	[19]
Sn-Cu	合金化	84.4	79	[25]
Pb₁Cu	合金化	96	1000	[18]
Cu₂S/Cu	硫掺杂	85	5.3	[26]
超薄多孔Cu-S NFs	硫掺杂	89.8	404.1	[27]
磷酸盐调控Cu	磷掺杂	79	—	[28]
Cu₂O(111)	晶面暴露	90	—	[29]
Cu₂O (100)	晶面暴露	90	260	[30]
Cu@NC	氮掺杂碳材料	41	—	[31]
Cu₂S/ NDg-C₃N₄	含氮缺陷的石墨相氮化碳	82.3	5.24	[32]
Cu-CDots	碳点载体	79	—	[33]

催化剂	策略	$F E H C O O -$ /%	电流密度/mA·cm^-2	参考文献
多孔树枝Cu	形貌调整	87	6.5	[21]
三维核壳Cu@Sn	形貌调整	100	16.52	[22]
中空纤维Cu	形貌调整	77.1	34.7	[23]
Pd₅Cu₁	合金化	64	—	[24]
CdCu@Cu	合金化	70.5	30.5	[19]
Sn-Cu	合金化	84.4	79	[25]
Pb₁Cu	合金化	96	1000	[18]
Cu₂S/Cu	硫掺杂	85	5.3	[26]
超薄多孔Cu-S NFs	硫掺杂	89.8	404.1	[27]
磷酸盐调控Cu	磷掺杂	79	—	[28]
Cu₂O(111)	晶面暴露	90	—	[29]
Cu₂O (100)	晶面暴露	90	260	[30]
Cu@NC	氮掺杂碳材料	41	—	[31]
Cu₂S/ NDg-C₃N₄	含氮缺陷的石墨相氮化碳	82.3	5.24	[32]
Cu-CDots	碳点载体	79	—	[33]

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