Defective Dopant-Free TiO2 as an Efficient Visible Light-Active Photocatalyst

Pristine and modified/doped titania are still some of the most widely investigated photocatalysts due to its high activity, stability, abundance and proper redox properties to carry out various reactions. However, modifiers and/or dopants resulting in visible-light activity might be expensive or work as recombination centers under UV irradiation. It seems that defective titania, known as “self-doped” TiO2, might be the best solution since it can be obtained under mild conditions without the addition of expensive materials and methods. This review discusses various methods of defective titania preparation, characterization of defect types, their localization (surface vs. bulk) and their function, as well as proposed mechanisms of photocatalytic reactions in the presence of self-doped titania. Although many kinds of defective titania samples have already been prepared with different colors, color intensities and defect kinds (mainly Ti3+ and oxygen vacancies), it is difficult to conclude which of them are the most recommended as the preparation conditions and activity testing used by authors differ. Furthermore, activity testing under solar radiation and for dyes does not clarify the mechanism since bare titania can also be excited and sensitized, respectively, in these conditions. In many reports, authors have not considered the possible influence of some impurities originated from the synthesis method (e.g., H, Al, Zn, Cl, F) that could co-participate in the overall mechanism of photocatalytic reactions. Moreover, some reports indicate that defective titania, especially black ones, might decrease activity since the defects might work as recombination centers. Despite some unproven/unclear findings and unanswered questions, there are many well-conducted studies confirmed by both experimental and theoretical studies that defective titania might be a promising material for various photocatalytic reactions under both UV and visible-light irradiation. Based on available literature, it could be proposed that optimal defects’ concentration, the preferential role of surface defects, a higher surface-to-bulk ratio of defects in rutile than in anatase, and the beneficial impact of disordered surface are the most important aspects to be considered during the preparation of defective titania