Recent Advances in Carbon‐Supported Single‐Atom Electrocatalysts for CO2 Reduction Reaction: From Dynamic Evolution to Structural Heterogeneity Regulation

Abstract The electrochemical CO 2 reduction reaction (eCO 2 RR) offers a promising method for sustainable energy conversion, enabling the transformation of electrical energy into chemical energy while achieving carbon neutrality efforts. Among the various electrocatalysts, carbon‐supported single‐atom catalysts (C‐SACs) have garnered significant interest due to their advantages of high atom efficiency, tunable structure, and exceptional catalytic activity. Designing effective C‐SACs for eCO 2 RR requires a comprehensive understanding of their structure‐property relationship, particularly regarding the dynamic changes of these materials under electrochemical conditions. Despite recently achieved innovative progress, universal design guidelines remain elusive, and the development of ideal catalysts still highly relies on trial‐and‐error approaches. This review provides a detailed analysis of the real‐time structure evolution and mechanisms of C‐SACs during eCO 2 RR, integrating various in situ and operando techniques with theoretical analyses. Consequently, nine design strategies aimed at increasing structural heterogeneity through the modification of metal, nitrogen, and carbon components in C‐SACs, focusing on specific cases that elucidate the structure‐performance relationship, are highlighted. Finally, the existing challenges are addressed, and future directions for the advancement of efficient C‐SACs in eCO 2 RR are outlined. This review aspires to illuminate a promising path for researchers aiming to design high‐performance C‐SACs for sustainable eCO 2 RR initiatives.