Intrinsic intermediate gap states of TiO2 materials and their roles in charge carrier kinetics

Titanium dioxide (TiO2) is regarded as an important prototype photocatalytic material for several decades. The charge carrier kinetics determines the photocatalytic properties of TiO2 materials; this is found to be greatly dependent on electronic structures. It has been revealed that the intrinsic intermediate gap states (intrinsic GSs) play a significant role in charge carrier kinetics that drive the photocatalytic processes of TiO2 materials, which are not well summarized until now. Motivated by this thought, the purpose of this review focuses on physiochemical science of the intrinsic GSs of TiO2 materials and their important role in charge carrier kinetics. We first give a summary on the chemical resources of the intrinsic GSs in TiO2 and their physiochemical nature. Their general energy distribution, charge carrier population, and the associated thermodynamic properties are also elaborated from an overall viewpoint. We further carefully summarize and compare the experimental studies on the energy and the density distribution of the intrinsic GSs and discuss the associated chemical resources and charge carrier localizations. Trapping is the dominant function of intrinsic GSs in the charge carrier kinetics of TiO2 materials. The significant effect of trapping on the transport, recombination, and interfacial transfer of charge carriers are also comprehensive summarized. Furthermore, the effects of charge carrier kinetics on photocatalytic performances are also discussed to some extents. Because of the importance of intrinsic GSs in modulating charge carrier kinetics, it is expected to increase the photocatalytic activity by engineering the intrinsic GSs, not only for TiO2 materials, but also for the other semiconductor photocatalysts. (C) 2019 Published by Elsevier B.V.