Abstract
Nanostructured TiO2 samples with primary particle size in the 4−20 nm range were prepared by either hydrothermal (H) or thermal (T) treatment of an amorphous precursor, and their behavior under UV illumination at 77 K was studied by means of EPR spectroscopy. The samples of the H series present the smallest crystallite size and after irradiation in a vacuum show some Ti3+ centers. In contrast, under these conditions only weak signals associated with oxygenated radicals are observed for the T samples. However, when oxygen is preadsorbed, several oxygenated complexes (O-, O2-, O2H•, and O3-) are photogenerated in proportions that depend on the characteristics of the material. Subsurface O- species are exclusively detected in the case of the samples of the H series, whereas ozonide radicals and surface O- are stabilized on materials with larger crystalline domains. These oxygenated complexes are thermally unstable, and they disappeared after warming to room temperature in the case of the T samples, but they ...
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