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

Electrochemical reduction of CO (CO RR) into valuable hydrocarbons is appealing in alleviating the excessive CO level. We present the very first utilization of metallic bismuth-tin (Bi-Sn) aerogel for CO 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 FE of 93.9 %. Moreover, the Bi-Sn aerogel achieves a FE 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.