Insights into the dynamic evolution of catalytic active centers of the electrocatalytic carbon dioxide reduction reaction

In recent years, electrocatalytic CO2 reduction reaction (CO2RR) has attracted a great deal of research interest as a possible route for recycling CO2 into more valuable chemicals with the aim of a decarbonized society, where the identification of catalytic active centers and a deeper understanding of structure-performance relationships are the bases. Despite this, significant intrinsic variation occurs frequently during operation in catalytic materials such as copper-based catalysts, making determining the actual catalytic active centers and understanding the relationships between structure-property and associated catalytic functionality difficult. Identifying electroactive centers during the CO2RR is of particular importance in this study, which inspired the layout of this review. Firstly, the basic concepts of the dynamic evolution in CO2RR, comprising reaction thermodynamics and kinetics characteristics, are addressed, followed by an overview of operando characterization methodologies used to investigate the evolution in operational settings. The dynamic evolution characteristics of common catalytic materials, such as atomic rearrangements and changes in chemical states, have been extensively studied, with a particular focus on the relationships between these characteristics and electronic properties such as catalytic performance, product selectivity, and durability. Lastly, the developing CO2 pulse-mode electrolysis process that has the potential to alter evolution's kinetics and potential possibilities is highlighted.

Automated summary

In recent years, research interest in electrocatalytic CO2 reduction reaction (CO2RR) has grown due to its potential to recycle CO2 into valuable chemicals. However, determining the catalytic active centers and understanding structure-performance relationships in catalysts, such as copper-based catalysts, is challenging due to their intrinsic variation during operation. This review focuses on identifying electroactive centers in the CO2RR and discusses the dynamic evolution characteristics, operando characterization methodologies, and the potential of the CO2 pulse-mode electrolysis process.