Porphyrin-based metallo-organic cage for selective photocatalysis under heterogeneous and atmospheric conditions

Developing highly efficient and stable photocatalytic systems for selective oxidation reactions and biomimetic catalysis represents both a frontier and a challenge in current research. This work successfully designed and synthesized a novel porphyrin-based metallo-organic cage (MOC), Por-Cage, which has been thoroughly characterized by proton nuclear magnetic resonance (¹H NMR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction (SC-XRD). Photophysical and photoelectrochemical studies reveal that, compared to ligand L and tetraphenyltetrapyrrole (TPP), Por-Cage exhibits superior light absorption, significantly enhanced photogenerated charge separation efficiency, and reactive oxygen species (ROS) production due to its unique supramolecular architecture. Using the photocatalytic detoxification of 2-chloroethyl ethyl sulfide (CEES) as a model reaction, Por-Cage demonstrated outstanding heterogeneous catalytic activity, achieving highly efficient degradation with 100% selectivity under an air atmosphere after 20 minutes of illumination. Furthermore, it exhibited universal applicability toward the oxidation of sulfides in aromatic compounds. This study provides a novel design strategy for constructing high-performance MOC photocatalysts that eliminate the dependence on pure oxygen and demonstrates their potential applications in environmental detoxification and selective photocatalytic reactions.