Dynamic reconstruction of electrocatalysts during CO₂ reduction reactions

Electrochemical CO₂ reduction (CO₂RR) offers a promising route for the carbon-neutral production of value-added chemicals and fuels. A critical yet underexplored aspect is that the dynamic reconstruction of electrocatalysts during the electrochemical CO₂ reduction reaction represents a pivotal phenomenon, governing catalytic activity, selectivity, and stability toward value-added products. This review comprehensively presents the thermodynamic and kinetic driving forces, including atomic migration, redox transformations, and facet-dependent restructuring, which underpin catalyst evolution under operational conditions. We highlight how reconstructed surfaces cause critical active site defects, grain boundaries, and heterointerfaces, which dictate reaction pathways but also introduce vulnerabilities such as degradation. The strategic modulation approaches, such as heteroatom doping, electrolyte engineering, and pulsed electrolysis, are briefly addressed for their capacity to direct reconstruction toward enhanced performance. Critically, we underscore the role of advanced in situ/operando techniques such as XRD, XAS, Raman spectroscopy, and electrochemical microscopy in resolving real-time structural, compositional, and intermediate adsorption dynamics. Integrating these insights with theoretical modeling elucidates structure-property relationships, enabling rational design of robust catalysts. Finally, we identify emerging opportunities, including machine learning-guided dynamics prediction and self-healing materials, to address stability challenges. This review synthesizes current understanding to establish a foundational framework essential for harnessing dynamic reconstruction, ultimately advancing CO₂RR toward industrial viability.