Visible Light‐Driven Synthesis of a Bioinspired Porphyrin‐Based Polymer‐Coated MOF for Efficient and Selective Photocatalytic Oxidation of Vanillyl Alcohol to Vanillin

Abstract The development of metal–organic framework (MOF)‐polymer composites presents a promising avenue for designing advanced functional materials, yet preserving MOF porosity and stability after modification remains challenging. Here, the study synthesizes a MOF from cost‐effective precursors under mild conditions and functionalizes it in situ covalent porphyrinic polymer layer via visible‐light irradiation, eliminating the need for additional reagents. The resulting composite, CPhP@UiO‐66(Ce)‐NH ₂ , is extensively characterized using FT‐IR, XRD, SEM/EDX, HRTEM, BET, XPS, UV–vis DRS, EPR, transient absorption spectroscopy, and solid‐state ¹³ C NMR spectroscopy. Under low‐energy LED light, the composite efficiently generates reactive oxygen species (ROS), enabling the additive‐free aerobic oxidation of vanillyl alcohol (a lignin model monomer) to vanillin with high selectivity and conversion, outperforming both the parent MOF and reported systems. This work introduces a novel, biomimetic strategy for constructing macrocycle‐inspired MOF‐polymer hybrids, demonstrated for the first time in selective photocatalytic aerobic oxidation. The findings advance the design of MOF‐based materials for sustainable catalysis and green chemistry applications.