Tailoring Electronic Structures via Ce/C Co-Doping and Oxygen Vacancy in TiO2 Aerogels for Enhanced Solar Fuel Production

A targeted modification approach involving the synthesis of Ce/C co-doped TiO₂ aerogels (CeCTi) via a sol-gel method combined with supercritical CO₂ drying and subsequent heat treatment is employed to enhance the photocatalytic CO₂ reduction performance of cost-effective and stable TiO₂ aerogels. The results demonstrate that the CeCTi exhibits a pearl-like porous network structure, an optical band gap of 2.90 eV, and a maximum specific surface area of 188.81 m²/g. The black aerogel sample shows an enhanced light absorption capability resulting from the Ce/C co-doping, which is attributed to the formation of oxygen vacancies. Under simulated sunlight irradiation, the production rates of CH₄ and CO reach 27.06 and 97.11 μmol g^-1 h^-1 without any co-catalysts or sacrificial agents, respectively, which are 82.0 and 5.7 times higher than those of the pristine TiO₂ aerogel. DFT reveals that C-doping facilitates the formation of oxygen vacancies, which introduces defect states within the calculational band gap of TiO₂. The proposed photocatalytic mechanism involves the light-induced excitation of electrons from the valence band to the conduction band, their trapping by oxygen vacancies to prolong the charge carrier lifetime, and their subsequent transfer to adsorbed CO₂ molecules, thereby enabling efficient CO₂ reduction, which is experimentally supported by photoluminescence measurements.