Titanium dioxide (TiO2) has been intensively investigated for solar hydrogen conversion via photocatalytic and photoelectrochemical water splitting. However, the performance of TiO2 photocatalyst for hydrogen generation is low due to the rapid electron-hole recombination and its wide band gap (3.0-3.2 eV) which is only feasible for UV light absorption of solar spectrum. There are various strategies have been used for TiO2 modification to harvest the sunlight and improve the surface chemical reaction between TiO2 and H2O for water splitting. Among the TiO2 modification strategies, intrinsic point defects such as vacancies and interstitials in TiO2 have been proven to improve the TiO2 properties for photo-catalytic activity. In this article, the recent progress achieved in defective TiO2 with intrinsic point defects for photocatalytic hydrogen evolution and photoelectrochemical water splitting has been reviewed. The fabrication methods of defective TiO2 along with their structural, optical, and charge carrier properties have been introduced. It has appeared that the intrinsic point defects are a promising strategy to improve the performance of TiO2 for photocatalytic hydrogen production, and more efforts are still needed to improve the TiO2 performance for photocatalytic hydrogen production in this area of research.
