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

Catalysis of the conversion of CO₂ from industrial exhaust gases to methanol at dynamically varying concentrations using renewable electrical energy is crucial for reducing CO₂ emissions and producing valuable chemical feedstocks. However, the challenges associated with the weak activation of linear nonpolar CO₂ 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 (CuN₃-C) to achieve efficient electrocatalytic reduction of high- and low-concentration CO₂ to CH₃OH. For both high-concentration or low-concentration CO₂ used as the feedstock, the CuN₃-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 CuN₃-C catalyst facilitates more effective CO₂ activation and preferential *CO hydrogenation toward *CHO and *CHOH. This study provides a strategy for designing highly efficient catalysts for the conversion of CO₂ to methanol via electronic polarization modulation.