Singlet Oxygen Photocatalytic Generation by Silanized TiO 2 Nanoparticles.

A commercial TiO ₂ sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid-state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N ₂ physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti ³⁺ defects localized in the sub-surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O ₂ is efficiently inhibited even under UV irradiation. However, the amount of Ti ³⁺ centers appears to be correlated with the singlet oxygen ( ¹ O ₂ ) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by ¹ O ₂ , occurred with higher selectivity when TiO ₂ was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample ¹ O ₂ may be generated through Förster-type energy transfer from excited sub-surface Ti ³⁺ centers.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)