Oxygen vacancies in TiO2/SnOx coatings prepared by ball milling followed by calcination and their influence on the photocatalytic activity

We prepared TiO2/SnOx(x = 1, 2) composite coatings through ball milling followed by calcination. The composite coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), spherical aberration corrected scanning transmission microscopy (Cs-corrected STEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) and other techniques. Bulk oxygen vacancies in the form of vacancy clusters rather than individual sites were directly observed by Cs-corrected STEM. With an increase in the calcination temperature from 873 K to 1073 K or holding time from five hours to ten hours, the concentration of bulk defects also increased. On the other hand, the photocatalytic activity of the as-prepared samples for degrading MB dye increased with the concentration increase of bulk defects. Sample 973 K-10 h showed the best photocatalytic activity whether under the irradiation of UV light or visible light. With a further increase in the concentration of bulk oxygen vacancies, the photocatalytic activity decreased, although surface Ti3+ defects appeared. In other words, a moderate concentration of bulk defects could benefit the enhancement of the photocatalytic activity of the as-prepared samples. Ball milling followed by calcination is an effective method to introduce defects such as oxygen vacancies.