Shixia Chen, Lei Guo, Shanshan Fu, Yuhan Li, DongLiang Liu, Jun Wang
Precise design of electrocatalyst is crucial for advancing the electrochemical CO 2 reduction reaction (CO 2 RR), yet it is still impeded by incomplete understanding of structure-property relationships. Although substantial efforts have been devoted to enhancing activity and selectivity via rational catalyst design, the true nature of active sites under operational conditions often remains elusive. Importantly, monitoring and strategically controlling the dynamic reconstruction of electrocatalysts during operation are essential for elucidating reaction mechanisms and enabling the rational design of next-generation high-performance catalysts. Despite its critical importance, comprehensive reviews specifically addressing catalyst reconstruction in the context of CO 2 RR remain scarce. This review fills this gap by providing a systematic analysis of electrocatalyst reconstruction phenomena in CO 2 RR, focusing on three core interconnected aspects: (1) identifying the real active sites through unraveling their chemical and morphological evolution; (2) understanding the driving forces behind reconstruction, particularly key factors such as electrolyte composition and applied potential; and (3) exploring strategies to manipulate reconstruction by guiding dynamic structural changes for superior electrocatalyst engineering. The goal is to deepen the fundamental understanding of CO 2 RR reconstruction processes and provide actionable guidelines for designing advanced electrocatalysts.