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

Abstract Oxygen vacancies are usually thought to be beneficial for photogenerated charge separation. In this work, the oxygen vacancies in ov‐Bi 2 O 3 (Bi 2 O 3 with oxygen vacancy) were found to be able to produce 1 O 2 in the dark owing to chemical adsorption. The oxygen vacancies were further found to be responsible for ov‐Bi 2 O 3 exhibiting higher 1 O 2 generation under light irradiation with 1 O 2 as the only reactive oxygen species (ROS) than Bi 2 O 3 with 1 O 2 , H 2 O 2 , 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‐Bi 2 O 3 displayed better performance than Bi 2 O 3 , 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.