二氧化碳电还原的电解质研究进展

doi:10.11949/0438-1157.20220757

摘要/Abstract

摘要：

基于可再生能源电力将二氧化碳电化学还原（CO₂RR）为高价值化学品是实现二氧化碳资源化利用的有效途径。催化剂和电解质组分对界面微环境的调控共同决定了CO₂RR的催化性能。尽管在高性能催化剂的设计及制备方面已取得了实质性进展，但电解质组分对界面局部催化环境的影响，以及对CO₂RR反应过程的优化机理还未得到充分认识。综述了电解质组分对CO₂RR界面微环境调控的研究进展，重点围绕电解质中阳离子、阴离子、溶剂、配体以及添加剂等开展讨论，包括电解质组分对界面化学环境的影响，如界面电场、局部pH、偶极-场作用和界面水结构等，揭示电解质调控的反应机理，以及在改善催化性能中的重要作用。本文从电解质调控角度出发，为设计高催化性能电解体系提供新的研究思路，推动CO₂RR领域发展。

关键词: 二氧化碳, 电化学, 电解质, 界面, 局部微环境

Abstract:

Electrochemical reduction of CO₂ (CO₂RR) to high-value chemicals powered by renewable electricity is an effective way to realize the resourceful use of CO₂. The catalytic performance of CO₂RR is jointly determined by the electrocatalysts and electrolyte components. Despite significant advances in the design and preparation of high-performance catalysts, the impact of electrolyte components on the local catalytic environment at the interface and methods for optimising the CO₂RR process are still poorly understood. This paper reviews the research progress of electrolyte component modulation of the interfacial microenvironment during CO₂RR, focusing on cations, anions, solvents, ligands and additives in the electrolytes. These include the effects of electrolyte components on the interfacial chemical environment, such as interfacial electric field, local pH, dipole-field interaction and interfacial water structure, revealing the modulation mechanism of electrolytes and their important roles on improving the catalytic performance. From the perspective of electrolyte regulation, this paper provides new research ideas for designing electrolytic systems with high catalytic performance, and promotes the development of CO₂RR.

Key words: carbon dioxide, electrochemistry, electrolytes, interface, local microenvironment

中图分类号:

TQ 15

葛旺鑫, 朱以华, 江宏亮, 李春忠. 二氧化碳电还原的电解质研究进展[J]. 化工学报, 2022, 73(8): 3433-3447.

Wangxin GE, Yihua ZHU, Hongliang JIANG, Chunzhong LI. Research progress on electrolytes for carbon dioxide electroreduction[J]. CIESC Journal, 2022, 73(8): 3433-3447.

图/表 13

图1 基于GCS模型的EDL结构示意图[13](由紧密层（IHP和OHP层）和扩散层组成，黄色曲线表示电势与距离电极表面距离的关系。粉色、红色、灰色和黑灰色小球分别代表碱金属阳离子、氧原子、氢原子和碳原子)

Fig.1 Schematic illustration of the EDL structure based on Gouy-Chapman-Stern model[13]

图2 电解质组分对CO2RR界面微环境调控示意图

Fig.2 Diagrammatic sketch of the modulation of the interfacial microenvironment of CO2RR by electrolyte components

表1 碱金属阳离子在本体溶液以及Cu电极和Ag电极表面的水解pKa值［18］

Table 1 Hydrolysis pKa values of alkali metal cations in bulk solution and on the surface of Cu and Ag electrodes［18］

Cation	pK_a
Cation	Bulk	Cu (Surf)	Ag (Surf)
Li⁺	13.6	11.64	13.16
Na⁺	14.2	10.26	11.44
K⁺	14.5	7.95	8.49
Rb⁺	14.6	6.97	7.23
Cs⁺	14.7	4.31	4.32

图3 CO2RR的阳离子效应

Fig.3 Cation effect of CO2RR

图4 CO2RR的阴离子效应

Fig.4 Anionic effect of CO2RR

图5 CO2、H2CO3、HCO3-和CO32-的溶解度与pH的关系[56]

Fig.5 Solubility of CO2, H2CO3, HCO3-, and CO32- as a function of pH[56]

图6 CO2及其相关物质的Pourbaix图[57]

Fig.6 Pourbaix diagram of CO2 and its related substances[57]

图7 表面配体/添加剂对CO2RR界面的影响

Fig.7 Effects of surface ligands/additives on CO2RR interfaces

图8 非质子型溶剂中碳酸盐和CO的歧化反应机理（上）以及*CO2-二聚形成草酸盐机理（下）[86]

Fig.8 Suggested reaction mechanism for the disproportionation to carbonate and carbon monoxide (above) and the dimerization to oxalate (below) in aprotic media[86]

图9 在含不同有机溶剂的0.1 mol/L Bu4N+中的CV曲线[91]

Fig.9 Cyclic voltammograms recorded in 0.1 mol/L Bu4N+ in various solvents[91]

图10 CO2RR体系中典型离子液体的阳离子和阴离子[93]

Fig.10 Cations and anions of typical ionic liquid in the CO2RR system[93]

图11 离子液体的作用机制：相比于[H2O-CO2]构型，Emim-与CO2通过形成[Emim–CO2]络合物构型活化CO2[102]

Fig.11 Role of ionic liquid in CO2RR: Emim- and CO2 by forming [Emim-CO2] complex configuration compared to [H2O-CO2][102]

图12 含固态电解质的二氧化碳还原电池示意图[104]

Fig.12 Schematic illustration of the CO2 reduction cell with solid electrolyte[104]

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