Triple‐Phase Interface Engineered Hierarchical Porous Electrode for CO₂ Electroreduction to Formate

Abstract The aqueous electrochemical CO₂ reduction to valuable products is seen as one of the most promising candidates to achieve carbon neutrality yet still suffers from poor selectivity and lower current density. Highly efficient CO₂ reduction significantly relies on well‐constructed electrode to realize efficient and stable triple‐phase contact of CO₂, electrolyte, and active sites. Herein, a triple‐phase interface engineering approach featuring the combination of hierarchical porous morphology design and surface modification is presented. A hierarchical porous electrode is constructed by depositing bismuth nanosheet array on copper foam followed by trimethoxy (1H,1H,2H,2H‐heptadecafluorodecyl) silane modification on the nanosheet surface. This electrode not only achieves highly selective and efficient CO₂ reduction performance with formate selectivity above 90% over wide potentials and a partial current density over −90 mA cm⁻² in H‐cell but also maintains a superior stability during the long‐term operation. It is demonstrated that this remarkable performance is attributed to the construction of efficient and stable triple‐phase interface. Theoretical calculations also show that the modified surface optimizes the activation path by lowering thermodynamic barriers of the key intermediates *OCHO for the formation of formate during electrochemical CO₂ reduction.