Self-organized TiO2 nanotubular arrays for photoelectrochemical hydrogen generation:: effect of crystallization and defect structures

The effect of crystallization and surface chemistry of nanotubular titanium dioxide (TiO2) in connection with the photoelectrochemical process is reported in this investigation. TiO2 nanotubular arrays were synthesized by a simple anodization process in an acidified fluoride electrolyte at room temperature. The TiO2 nanotubes were amorphous in as-anodized condition; their transformation to crystalline phases was a function of annealing temperature and gaseous environment. The anatase phase was observed predominantly after annealing in non-oxidizing atmospheres, whereas annealing in an oxygen environment showed a mixture of anatase and rutile phases. X-ray photoelectron spectroscopy was used to determine the chemical environment of the surface, which revealed the presence of phosphate, oxygen vacancies and pentacoordinated Ti in hydrogen annealed samples. Diffuse reflectance photospectrometry of non-oxygen annealed samples showed long absorption tails extending in the visible region. The photoelectrochemical response of the TiO2 nanotubes annealed in different conditions was investigated. Photoelectrochemical performance under simulated solar light was improved by annealing the nanotubular TiO2 samples in non-oxidizing environment.