Structural Reconstruction of Copper-Based Catalysts in CO₂ Electroreduction Reaction: A Comprehensive Review

The escalating concerns over climate change and environmental pollution have intensified the pursuit for sustainable solutions to mitigate CO₂ emissions, with the electrochemical CO₂ reduction reaction (CO₂RR) emerging as a promising strategy to convert CO₂ into valuable chemicals and fuels. Central to this process is the development of efficient electrocatalysts, where Cu-based catalysts have garnered significant attention due to their high activity towards multi-carbon products. However, understanding of structural reconstruction of Cu-based catalysts under operational conditions presents a substantial challenge, complicating the identification of real active sites and the elucidation of structure-performance relationships. Herein, we first highlight the fundamental principles governing the structural reconstruction in CO₂RR, encompassing both thermodynamic and kinetic perspectives. We then introduce advanced Operando techniques employed to monitor the structural changes of catalysts. The review further delves into the dynamic evolution behaviors of Cu-based catalysts, including atomic rearrangement and morphology evolution, with a focus on correlating these behaviors with catalytic properties such as activity, selectivity, and stability. Finally, we discuss cases of emerging strategies, such as heteroatom doping and electrolyte engineering, that hold promise for manipulating the structural reconstruction of Cu-based catalysts, and we explore future opportunities in this rapidly evolving field.