In recent decades, the excessive consumption of fossil fuels has significantly exacerbated environmental problems such as the greenhouse effect. Consequently, the development of efficient carbon dioxide capture and utilization technologies is particularly urgent. The electrochemical CO 2 reduction reaction (eCO 2 RR) has emerged as a highly promising strategy for converting CO 2 into high-value chemicals. Alkali metal ions in the electrolyte play a pivotal role in this process, including enhancing catalytic activity and regulating product selectivity. However, the mechanisms by which alkali metal cations modulate the electrocatalytic reaction process, as well as the core determinants underlying the alkali metal cation effect, remain controversial issues in the field.
Currently, the majority of research on the regulatory effects of alkali metal cations in eCO 2 RR centers on the correlation between catalytic performance and qualitative spectral characterization, or on idealized calculations of the electrode-electrolyte interfacial microenvironment and simplified electric double layer models. The primary focus has been on the influences of variables such as the concentration and type of alkali metal cations on eCO 2 RR performance. However, underlying investigations into the effects of alkali metal cation distribution patterns on interfacial physicochemical properties, reaction kinetics, and thermodynamics remain scarce. Moreover, the intrinsic quantitative relationship between catalytic performance and alkali metal cations, the physicochemical origin of the alkali metal cation effect remains unclear.
Recently, a research team led by Prof. You-Nian Liu & Dr. Shanyong Chen (Central south university) have systematically summarized the recent advances in the research on the role of alkali metal cations in eCO 2 RR, reviewed the recent advancements in modern electric double layer theory, clarified three distinct distribution patterns of alkali metal cations at the reaction interface, which correspond to three interfacial adsorption modes of alkali metal cations: electrostatic adsorption, specific adsorption, and quasi-specific adsorption. Furthermore, the team discussed the influences of system variables on the adsorption modes of alkali metal cations, as well as the regulatory mechanisms of different adsorption modes on eCO 2 RR, and clarified the physicochemical origin of the alkali metal cation effect. Subsequently, they systematically summarized the specific action mechanisms of these cations in different electrolyte systems, along with the regulatory roles of other analogous nitrogen-containing organic cations (which contain alkali metal cation-like properties) in eCO 2 RR and their potential to assist or replace alkali metal cations in eCO 2 RR processes. Finally, based on the latest insights into the effects of alkali metal cations, the team proposed the basic viewpoints and prospects for future research, providing important references for the rational design of next-generation advanced eCO 2 RR electrolysis systems.The results were published in Chinese Journal of Catalysis (DOI: 10.1016/S1872-2067(25)64834-0 ).
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Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top one journals in Applied Chemistry with a current SCI impact factor of 17.7. The Editors-in-Chief are Profs. Can Li and Tao Zhang.
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Chinese Journal of Catalysis
Alkali cation effects in electrochemical carbon dioxide reduction
8-Jan-2026