Visible-Light-Driven Photocatalytic Hydrogen Generation on Nanosized TiO2-II Stabilized by High-Pressure Torsion

Photocatalytic activity of pure TiO2 is limited to ultraviolet (UV) light due to the wide bandgap of anatase and rutile phases. The bandgap of high-pressure phases of TiO2 can theoretically coincide with visible light, but these phases are unstable at ambient pressure. In this work, the high-pressure TiO2-II (columbite) phase with large fractions of oxygen vacancies was stabilized by inducing plastic strain to anatase under 6 GPa. The material could absorb visible light as a consequence of bandgap narrowing by ∼0.7 eV. Formation of nanosized TiO2-II enhanced the hydrogen generation efficiency under visible light, and the efficiency improved after removing the oxygen vacancies by annealing.