Orbital Interactions in Bi‐Sn Bimetallic Electrocatalysts for Highly Selective Electrochemical CO₂ Reduction toward Formate Production

Abstract A highly selective and durable electrocatalyst for carbon dioxide (CO₂) conversion to formate is developed, consisting of tin (Sn) nanosheets decorated with bismuth (Bi) nanoparticles. Owing to the formation of active sites through favorable orbital interactions at the Sn‐Bi interface, the Bi‐Sn bimetallic catalyst converts CO₂ to formate with a remarkably high Faradaic efficiency (96%) and production rate (0.74 mmol h⁻¹ cm⁻²) at −1.1 V versus reversible hydrogen electrode. Additionally, the catalyst maintains its initial efficiency over an unprecedented 100 h of operation. Density functional theory reveals that the addition of Bi nanoparticles upshifts the electron states of Sn away from the Fermi level, allowing the HCOO* intermediate to favorably adsorb onto the Bi‐Sn interface compared to a pure Sn surface. This effectively facilitates the flow of electrons to promote selective and durable conversion of CO₂ to formate. This study provides sub‐atomic level insights and a general methodology for bimetallic catalyst developments and surface engineering for highly selective CO₂ electroreduction.