2D Ti-based metal–organic framework photocatalysis for red light-driven selective aerobic oxidation of sulfides

Ti-based metal-organic frameworks (MOFs) consisting of organic linkers and Ti-oxo clusters have tremendous proneness in visible light photocatalysis. Here, two-dimensional (2D) Ti-based porphyrin MOF (PMOF (Ti)) and bulk PMOF (Ti) were synthesized and fully characterized. Consequently, the porphyrin linker imparts broad absorption of visible light and the appropriate reduction potential of Ti‐oxo clusters can activate O2 to superoxide (O2•–). The 2D PMOF (Ti) exhibits more satisfying results for the red light-driven selective oxidation of sulfides with O2 than bulk PMOF (Ti). In addition, 2D PMOF (Ti) is highly robust which could be recycled 8 times without any loss of photocatalytic activity. Mechanistic investigations reveal that O2•– is the crucial reactive oxygen species (ROS) in forming sulfoxides with high selectivities. This work highlights that 2D MOFs could have a great potential in selective photocatalytic transformations of organic molecules.