Photoelectrochemical Water Splitting of Nitrogen and Hydrogen Treated P25 TiO2 Films

Photoelectrochemical data is reported for P25 TiO2/ films deposited as a pristine film on FTO. The pristine P25 films show a photocurrent of 0.06 mA/cm2 and an onset potential of -0.5 V vs. Ag/AgCl. After TiCl4 Treatment to form a compact TiO2 layer on the bottom and the surface layer, the TiCl4 sandwich films have a photocurrent of 0.19 mA/cm2 and an onset potential of -0.8 V. We have also investigated the effects of hydrogen treatment, ammonia treatment, and the combination of hydrogen treatment followed by ammonia treatment (co-treatment) on the photocurrent, the incident photon-to-current efficiency (IPCE), and the electron donor density of the P25 TiCl4 sandwich films. Treating the P25 films had almost no effect on the size and d-spacing of the particles, but EPR evidence, as well as color change, indicated the formation of N 2p nitrogen sites and oxygen vacancies (VO) for each film treatment. I-V data for the treated TiCl4 sandwich films show an increase in photocurrent from 0.19 mA/cm2 for the pristine P25 TiO2 film to 0.4 mA/cm2 for the co-treated TiO2 film compared to 0.23 mA/cm2 for hydrogen treatment and 0.25 mA/cm2 for ammonia treatment. For the P25 treated films, there is negligible increase of UV absorption in the visible for the singly treated films as well as the co-treated films. However, the improved photocurrent for the ammonia treated, hydrogen treated, and co-treated films may be explained by increased donor density. Mott-Schottky plots are used to characterize donor density, showing that the co-treated P25 TiCl4 sandwich films have an increased donor density over the nitrogen-treated P25 TiO2 and pristine P25 TiO2 films. The improved donor density of the treated P25 films over the untreated films may prove to be useful when completing future dye or semiconducting quantum dot sensitization experiments