Reconstruction of Transition Metal Catalysts for Industrial‐Scale Electrochemical CO 2 Reduction Under Operational Modulation

The reconstruction of catalysts during the electrochemical CO 2 reduction reaction (eCO 2 RR) is pivotal for carbon utilization and renewable energy storage. Driven by thermodynamic and kinetic forces, catalysts undergo inevitable dynamic evolutions that generate performance‐determining active sites. Traditional studies, however, often treat catalysts as static systems and overlook their real‐world working behavior, leading to biased understandings of active sites. To bridge this gap, this review proposes a tripartite framework demonstrating that catalyst evolution is a coupled, multiscale process driven by intrinsic chemical reconstruction, microenvironmental fluctuation, and external mechanical stress. Mechanistically, we reveal that intense local electric fields and pH gradients at high current densities accelerate surface atom migration, while physical stresses from vigorous bubble nucleation and growth trigger a vicious cycle of catalyst layer delamination and performance decay. We highlight how in situ characterizations and multiscale simulations resolve these stress‐coupled dynamics in real time, and summarize concrete stabilization strategies: employing precise coordination engineering and valence modulation to thermodynamically anchor active phases against migration, and utilizing interfacial texturing to enhance mechanical robustness against gas‐evolution stress. By bridging atomic‐scale reconstruction with device‐level failure modes, this review guides the rational design of durable catalysts for industrial eCO 2 RR.