Ultrathin Ti-doped WO3 nanosheets realizing selective photoreduction of CO2 to CH3OH

Abstract

Arduous CO₂ activation and sluggish charge transfer retard the photoreduction of CO₂ to CH₃OH with high efficiency and selectivity. Here, we fabricate ultrathin Ti-doped WO₃ nanosheets possessing approving active sites and optimized carrier dynamics as a promising catalyst. Quasi in situ X-ray photoelectron spectroscopy and synchrotron–radiation X-ray absorption near-edge spectroscopy firmly confirm that the true active sites for CO₂ reduction are the W sites rather the Ti sites, while the Ti dopants can facilitate charge transfer, which accelerates the generation of crucial COOH* intermediates as revealed by in situ Fourier-transform infrared spectroscopy and density functional theory calculations. Besides, the Gibbs free energy calculations also validate that Ti doping can lower the energy barrier of CO₂ activation and CH₃OH desorption by 0.22 eV and 0.42 eV, respectively, thus promoting the formation of CH₃OH. In consequence, the Ti-doped WO₃ ultrathin nanosheets show a superior CH₃OH selectivity of 88.9% and reach a CH₃OH evolution rate of 16.8 μmol g⁻¹ h⁻¹, about 3.3 times higher than that on WO₃ nanosheets. This work sheds light on promoting CO₂ photoreduction to CH₃OH by rational elemental doping.