Oxygen-Vacancy-Enhanced Singlet Oxygen Production for Selective Photocatalytic Oxidation

Oxygen vacancies are usually thought to be beneficial for photogenerated charge separation. In this work, the oxygen vacancies in ov-Bi₂ O₃ (Bi₂ O₃ with oxygen vacancy) were found to be able to produce ¹ O₂ in the dark owing to chemical adsorption. The oxygen vacancies were further found to be responsible for ov-Bi₂ O₃ exhibiting higher ¹ O₂ generation under light irradiation with ¹ O₂ as the only reactive oxygen species (ROS) than Bi₂ O₃ with ¹ O₂ , H₂ O₂ , and others as the ROS. The photocatalytic activity was investigated for the selective photo-oxidation of phenyl methyl sulfide to phenyl methyl sulfoxide and phenyl alcohol to benzaldehyde. In either case, ov-Bi₂ O₃ displayed better performance than Bi₂ O₃ , suggesting the significant role of oxygen vacancies in modulating the photocatalytic oxidation properties. This work provides an alternative approach to obtain singlet oxygen, which may guide further design of photocatalysts with high efficiency and selectivity towards photocatalytic organic synthesis.