Oxygen Vacancies in the Spotlight: On the Engineering of Intrinsic Defects in Highly Defective Tio2 Photocatalysts

Nanostructured oxide semiconductors are widely used in energy conversion, catalysis, sensing and environmental applications, due to their high stability, commercial availability, efficiency and low cost. Despite its crucial importance for the design of more efficient materials, the interplay between intrinsic and extrinsic defects is yet to be clarified. For example, oxygen vacancies (VO’s) can be either beneficial or detrimental to the desired performances, depending on a variety of factors. Here, we synthesize TiO2-x samples by the addition of three different N chemical sources (NH3, triethylamine, urea). X-ray absorption spectroscopy, confocal microscopy, UV–vis absorbance and fluorescence, are employed to explore the occurrence and location of VO’s both in real and energy spaces. High–grade bulk DFT simulations complement the experimental picture. Synergy between theory and experiment, on the one hand, estimates the relative VO’s content in the different samples from local structural information. On the other hand, a sharp optical transition at ≈2.7 eV serves an unequivocal spectral signature of bulk VO’s, allowing a semi-quantitative analysis by confocal microscopy. Surface oxygen vacancies do not display fluorescence features under UV pumping, possibly due to the reaction of surface defects with atmospheric O2. Thus, the comparison between local structure and confocal microscopy can discriminate surface-localized and bulk VO’s. Concurrently, UV-induced photochromism and visible light photodegradation shed light on the most effective reactive defects. Eventually, surface-localized oxygen vacancies are predominant where actual N substitutional doping occurs, leading to materials exhibiting visible-light activity and characteristic photochromic behaviour. Implications on strategies for concomitant VO engineering and extrinsic doping are discussed.