Visualizing CO ₂ Electroreduction Dynamics: Advances in Electrochemical AFM for Catalyst Interfacial Analysis

Electrochemical CO 2 reduction (CO 2 RR) stands as a transformative pathway for the sustainable synthesis of fuels and chemicals, yet its advancement is hindered by an incomplete mechanistic picture of dynamic catalyst evolution at the electrode‐electrolyte interface. This review emphasizes the critical role of in situ electrochemical atomic force microscopy (EC‐AFM) in addressing this knowledge gap. As a non‐invasive technique capable of nanometer‐ to near‐atomic scale resolution under operando conditions, EC‐AFM provides direct, real‐time visualization of catalyst dynamics. The review begins by outlining the fundamental principles and advantages of EC‐AFM for probing liquid‐solid interfaces and then systematically demonstrates its applications across major catalyst systems. These range from revealing potential‐dependent reconstruction and roughening on single‐crystal and polycrystalline copper electrodes, to tracking the stability and synergistic effects in Cu‐based bimetallic catalysts, and to elucidating structure‐activity dynamics in emerging systems such as gas diffusion electrodes. Finally, we discuss current technical challenges of EC‐AFM and propose future interdisciplinary research directions. This review summarizes how in situ EC‐AFM has informed our understanding of CO 2 RR by revealing dynamic catalyst reconstruction, tracking active‐site evolution, and elucidating interfacial processes. By systematically compiling these advances, it serves as a critical interdisciplinary resource, positioning EC‐AFM as a practical tool that offers visual guidance for the rational design of next‐generation catalysts and electrochemical systems.