A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide

Green and environmental protection has been of particular concern in modern chemistry research. In this work, we report a visible‐light photocatalytic molecular reactor based on a novel zirconium metal‐organic framework (Zr‐MOF) for the aerobic oxidation of sulfide to sulfoxide in water. The Zr‐MOF is constructed from perylenediimides‐based (PDI) carboxylate ligand and [Zr6O8(H2O)8]8+ clusters, and features a 3D (4,8)‐connected csq topological structure with triangular channels of ~5 Å and mesoporous hexagonal channels of ~26 Å along c‐axis. Interestingly, this Zr‐MOF exhibits visible‐light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor in water. When it is used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light in water, the Zr‐MOF could afford the corresponding sulfoxides with high yield, selectivity and superior recyclability. Furthermore, the mechanism studies revealed that the singlet oxygen (1O2) and superoxide radical (O2·‐) are the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI‐based MOFs for further study on photocatalytic reactions.