Electric field-driven one-step formation of vertical p–n junction TiO2 nanotubes exhibiting strong photocatalytic hydrogen production†
In this study, vertically aligned p–n junction TiO2 nanotubes can be formed by anodization of the Ti substrate following the addition of a high electric field in a Pd precursor-containing electrolyte. The bottom region of the TiO2 nanotubes with a high concentration of Pd because of the high electric field which was induced to be p-type. In contrast, the region with a low Pd concentration (top of the TiO2 nanotubes) was determined to be n-type, similar to the pristine TiO2. The concentration profile of the dopant in TiO2 nanotubes was investigated via TOF-SIMS and XPS. Defect formation energies in TiO2 nanotubes were estimated using density-functional theory calculation to understand the p–n junction formation. The p–n junction TiO2 nanotubes showed a high photocatalytic hydrogen production rate of 25.2 μL cm−2 h−1 under solar light irradiation as a result of the enhancement of visible light photoactivity.