Balanced Adsorption Toward Highly Selective Electrochemical Reduction of CO ₂ to Formate

Abstract Tin‐based materials have been designed as potential catalysts for the electrochemical conversion of CO ₂ into a single product. However, such tin‐based materials still face the challenges of unsatisfactory selectivity, because the rate‐determining step is situated within the slow desorption step. In this work, a variety of tin‐based materials are synthesized using the electrospinning technique in an effort to control the adsorption strength during electrochemical reduction, therefore improving the selectivity of CO ₂ reduction toward formate. The optimized SnS material exhibits moderate adsorption strength to *OCHO and *HCOOH, and the appropriate atomic distance of Sn–Sn maintained the balanced adsorption posture of both intermediate. Therefore, the rate‐determining step can be shifted from the slow desorption of the *HCOOH step (Sn) to the first hydrogenation of the *OCHO species step (SnS). Due to this shift, the SnS/C electrode demonstrated excellent selectivity, with a Faradaic efficiency of 96% for the production of formate. A maximum current density of −12.5 mA cm ⁻² for formate is also achieved for a period of 33 h.