Stability Issues in Electrochemical CO₂ Reduction: Recent Advances in Fundamental Understanding and Design Strategies

Abstract Electrochemical CO₂ reduction reaction (CO₂RR) offers a promising approach to close the anthropogenic carbon cycle and store intermittent renewable energy in fuels or chemicals. On the path to commercializing this technology, achieving the long‐term operation stability is a central requirement but still confronts challenges. This motivates to organize the present review to systematically discuss the stability issue of CO₂RR. This review starts from the fundamental understanding on the destabilization mechanisms of CO₂RR, with focus on the degradation of electrocatalyst and change of reaction microenvironment during continuous electrolysis. Subsequently, recent efforts on catalyst design to stabilize the active sites are summarized, where increasing atomic binding strength to resist surface reconstruction is highlighted. Next, the optimization of electrolysis system to enhance the operation stability by maintaining reaction microenvironment especially mitigating flooding and carbonate problems is demonstrated. The manipulation on operation conditions also enables to prolong CO₂RR lifespan through recovering catalytically active sites and mass transport process. This review finally ends up by indicating the challenges and future opportunities.