Electron Cloud Polarization of Single-Atom Cu Boosts Electrocatalytic Reduction of High- and Low-Concentration CO2 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.