Infrared and Thermo Co‐Driven Catalysis for CO 2 Conversion to Valuable Chemicals

Abstract Conversion of CO 2 into high value chemicals presents a promising pathway for CO 2 mitigation and utilisation. The direct synthesis of dimethyl carbonate from CO 2 and methanol is one of such carbon‐neutral pathways. However, thermal catalytic processes for direct dimethyl carbonate synthesis have reached a performance bottleneck at elevated temperatures. This work explores the synergy of photon and thermal energy to enhance the dimethyl carbonate production rate to 30 mmol/g/h, together with 100% selectivity, thanks to a defect‐modified and noble‐metal free cerium oxide catalyst. Fundamentally, it is found that the defects in cerium oxide can provide energy levels that enable IR light absorption and generate holes with a moderate oxidation potential, so avoiding the unfavorable overoxidation pathway and enhancing the production rate of dimethyl carbonate. The thermal energy has been proved to remarkably facilitate the relaxation of IR‐induced charge carriers and to enhance the dimethyl carbonate formation process. This work introduces a strategy of IR photons and thermo co‐driven catalysis and achieves a breakthrough in dimethyl carbonate formation.