Cu Anchored Carbon Nitride (Cu/CN) Catalyzes Selective Oxidation of Thiol by Controlling Reactive Oxygen Species Generation

Abstract

Production of H₂O₂ using heterogeneous semiconductor photocatalysts has emerged as an ecofriendly and practical approach across various applications, ranging from environmental detoxification to fuel cells and chemical synthesis. Extensive efforts have been devoted to engineering semiconductors to enhance their catalytic capabilities for H₂O₂ production. However, in chemical synthesis, the utilization of the potent oxidant H₂O₂ can present challenges in selectively oxidizing organic compounds. In this study, we introduce copper atoms into carbon nitride (Cu/CN), facilitating the generation of hydroperoxyl radicals (·OOH) as primary reactive oxidants and offering reaction conditions entirely devoid of H₂O₂ via the Fenton reaction. Cu/CN demonstrates selective oxidation of thiols to disulfides, in contrast to other current heterogeneous photocatalysts that yield undesired overoxidized side products, such as thiosulfinate and thiosulfonate. Cu/CN’s controllable capacity for specific ROS generation, broad substrate scopes, and recyclability empower greener and highly selective photooxidation of organic compounds.