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.