LAUSR

Abstract In this work, the oxygen defect strategy was conducted to promote photo-splitting H2S into hydrogen (H2) on the typical anatase TiO2 with active {0 0 1} facet for the first time. Density functional theory (DFT) calculation results illustrate that surface oxygen vacancy can efficiently facilitate the electron transition across the forbidden band and enhance the surface adsorption ability with more negative adsorption energies of −0.82 to −2.85 eV for H2S and its fragments than that of 0.24 to −0.90 eV on the perfect surface. Importantly, the energy barrier is reduced by 1.58 eV in maximum along the reaction paths on the defected surface, and the changes of rate-determining step lead to H2 as the final product. In addition, the time-resolved fluorescence tests, photocurrent measurements and electrochemical impedance spectroscopy demonstrate that the oxygen vacancies can effectively separate photo-generated electron-hole pairs. As a result, the photocatalytic activities of H2 evolution from H2S on TiO2 {0 0 1} doped with oxygen vacancies have been significantly enhanced from 21.44 μmol g−1 h−1 to 95.25 μmol g−1 h−1. This enhanced photoactivity is due to the low recombination of photo-generated carriers, the favorable surface adsorption and reaction activity induced by oxygen vacancies.