Electron Cloud Polarization of Single‐Atom Cu Boosts Electrocatalytic Reduction of High‐ and Low‐Concentration CO ₂ to Methanol

ABSTRACT Catalysis of the conversion of CO 2 from industrial exhaust gases to methanol at dynamically varying concentrations using renewable electrical energy is crucial for reducing CO 2 emissions and producing valuable chemical feedstocks. However, the challenges associated with the weak activation of linear nonpolar CO 2 molecules and the high energy difference of key proton‐coupled electron transfer steps make it difficult for existing catalysts to simultaneously achieve a high current density and a high selectivity. Herein, we report a strategy for regulating electron polarization in a Cu single‐atom catalyst (CuN 3 ‐C) to achieve efficient electrocatalytic reduction of high‐ and low‐concentration CO 2 to CH 3 OH. For both high‐concentration or low‐concentration CO 2 used as the feedstock, the CuN 3 ‐C catalyst achieves a current density exceeding −450 mA cm −2 , a Faradaic efficiency of 80% for methanol production, and record‐high production rate of 0.57 µmol s −1 cm −2 . In situ characterization and theoretical calculations jointly show that strong electron polarization of the CuN 3 ‐C catalyst facilitates more effective CO 2 activation and preferential *CO hydrogenation toward *CHO and *CHOH. This study provides a strategy for designing highly efficient catalysts for the conversion of CO 2 to methanol via electronic polarization modulation.