In Situ Meso-Tetra (4-Carboxyphenyl) Porphyrin Ligand Substitution in Hf-MOF for Enhanced Catalytic Activity and Stability in Photoredox Reactions

Though there are numerous intrinsic merits of metal-organic frameworks (MOFs), low charge separation efficiency has imposed heavy restrictions on their photocatalytic application. Herein, in situ porphyrin ligand substitution, as a strategy for improving the charge separation efficiency and increasing the amounts of active sites, has been designed and realized in a Hf-biphenyl dicarboxylic acid (BPDC) MOF. Specifically, a size and geometry matched meso-tetra (4-carboxyphenyl) porphyrin (TCPP) ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers, forming dual-ligand Hf-BPDC-TCPP MOF. The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H2 generation (261 μmol·g−1·h−1) and tetracycline (TC) degradation reactions (95.8