Application of a novel biomimetic double-ligand zirconium-based metal organic framework in environmental restoration and energy conversion

The development of visible-light response photocatalysts with a high catalytic performance and long-term cyclic stability is of great significance in the field of energy and environmental protection. Inspired by photosynthesis, a novel three-dimensional coral zirconium-based metal organic framework (MOF) was synthesized using a double-ligand strategy. The optimal sample, Zr-TCPP-bpydc (2:1), (the ratio of tetra-(4-carboxyphenyl) porphyrin to 2,2'-bipyridine-5,5'-dicarboxylic acid is 2:1) shows an excellent photocatalytic activity under visible light irradiation, and the effects of the amount of photocatalyst, pH and concentration on the degradation rate were investigated under the optimum conditions. It has a high degradation rate of tetracycline (98.12% for tetracycline and 96.74% for ofloxacin), which is 2.11 times higher than that of single ligand Zr-bpydc (zirconium-based MOF containing only 2,2'-bipyridine-5,5'-dicarboxylic acid). More importantly, it also has a good H2 evolution rate (213.68 μmol g-1h-1) and CO2 reduction (35.81 μmol g-1h-1). In addition, the intermediate pathway of degradation, photocatalytic enhancement mechanism and cycle stability were deeply studied by liquid chromatography-mass spectrometry (LC-MS), electron spin resonance spectroscopy (ESR), linear sweep voltammetry (LSV) and recycling tests. The synthesis of a three-dimensional biomimetic coral zirconium-based MOF material will provide guidance for the development of new, promising, and natural ideal photocatalytic materials.