Charge reaction kinetics on TiO2 nanotubes under photoelectrochemical water oxidation condition

Artificial photosynthesis relies on the photoreactions between the chemical molecules and photogenerated charges. The oxygen evolution reactions are regarded as the most difficult procedure, because they are multiple-step reactions with multiple charges transfer. Notwithstanding the extensive study on photoelectrochemical and photochemical water oxidation, understanding how the surface charge reacts with the chemical molecules is limited, especially the reaction kinetics of the surface charges. We prepared anatase TiO 2 nanotubes array and dense polycrystalline TiO 2 films on Ti substrates, where the photocurrent increased about 4–4.5 times on nanotubes compared with the dense films. Moreover, the surface charge reaction rate and the accumulated charge densities were analyzed by transient surface photovoltage and transient photocurrent techniques. It was found a 2nd-order charge reaction behavior could be found when the charge density was high, differently, a 1st-order charge reaction could be observed when the charge density was low. The nanotubes structures would in situ grow from the Ti substrates, which simultaneously enhanced charge separation and transfer kinetics to improve the PEC performance.