Engineering Bismuth–Tin Interface in Bimetallic Aerogel with a 3D Porous Structure for Highly Selective Electrocatalytic CO₂ Reduction to HCOOH

Electrochemical reduction of CO₂ (CO₂ RR) into valuable hydrocarbons is appealing in alleviating the excessive CO₂ level. We present the very first utilization of metallic bismuth-tin (Bi-Sn) aerogel for CO₂ RR with selective HCOOH production. A non-precious bimetallic aerogel of Bi-Sn is readily prepared at ambient temperature, which exhibits 3D morphology with interconnected channels, abundant interfaces and a hydrophilic surface. Superior to Bi and Sn, the Bi-Sn aerogel exposes more active sites and it has favorable mass transfer properties, which endow it with a high FEHCOOH of 93.9 %. Moreover, the Bi-Sn aerogel achieves a FEHCOOH of ca. 90 % that was maintained for 10 h in a flow battery. In situ ATR-FTIR measurements confirmed that the formation of *HCOO is the rate-determining step toward formic acid generation. DFT demonstrated the coexistence of Bi and Sn optimized the energy barrier for the production of HCOOH, thereby improving the catalytic activity.