Cu Anchored Carbon\nNitride (Cu/CN) Catalyzes Selective\nOxidation of Thiol by Controlling Reactive Oxygen Species Generation

Production of H<sub>2</sub>O<sub>2</sub> using heterogeneous\nsemiconductor\nphotocatalysts has emerged as an ecofriendly and practical approach\nacross various applications, ranging from environmental detoxification\nto fuel cells and chemical synthesis. Extensive efforts have been\ndevoted to engineering semiconductors to enhance their catalytic capabilities\nfor H<sub>2</sub>O<sub>2</sub> production. However, in chemical synthesis,\nthe utilization of the potent oxidant H<sub>2</sub>O<sub>2</sub> can\npresent challenges in selectively oxidizing organic compounds. In\nthis study, we introduce copper atoms into carbon nitride (Cu/CN),\nfacilitating the generation of hydroperoxyl radicals (·OOH) as\nprimary reactive oxidants and offering reaction conditions entirely\ndevoid of H<sub>2</sub>O<sub>2</sub> via the Fenton reaction. Cu/CN\ndemonstrates selective oxidation of thiols to disulfides, in contrast\nto other current heterogeneous photocatalysts that yield undesired\noveroxidized side products, such as thiosulfinate and thiosulfonate.\nCu/CN’s controllable capacity for specific ROS generation,\nbroad substrate scopes, and recyclability empower greener and highly\nselective photooxidation of organic compounds.