Highly Selective Electrochemical Reduction of CO 2 to Alcohols on an FeP Nanoarray

Abstract Electrochemical reduction of CO 2 into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO 2 reduction reaction to convert CO 2 into alcohols with high selectivity. In 0.5 m KHCO 3 , such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE ) up to 80.2 %, with a total FE of 94.3 % at −0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO 2 toward CH 3 OH owing to the synergistic effect of two adjacent Fe atoms, and the potential‐determining step is the hydrogenation process of *CO.