Photothermal Catalysis for Selective CO₂ Reduction on the Modified Anatase TiO₂ (101) Surface

Solar-induced photothermal catalysis of the CO2 reduction reaction (CO2RR) is a promising method for chemical CO2 conversion. Modification of the metal oxide catalyst surface, including the introduction of oxygen vacancies and the doping and loading of metal or metal oxides, has a considerable influence on the product selectivity of the CO2RR. The complete free energy profiles of the CO2RR pathway on modified anatase TiO2 (101) surfaces are calculated based on density functional theory. The modified surfaces enhance the adsorption of CO2, and competition between desorption and reduction of the key intermediates (CO*, HCOOH*, HCHO*, and CH3OH*) is crucial to the selectivity for the CO2RR to form C1 products. The loading of Au and the doping of MgO enhance the electron transfer between the key intermediates and the surface, as well as the internal electron transfer inside the key intermediates, which efficiently activates the key intermediates and significantly increases the CH4 selectivity of the CO2RR.