Removal of aqueous pharmaceuticals by magnetically functionalized Zr-MOFs: Adsorption Kinetics, Isotherms, and regeneration.

The functionalization of metal-organic frameworks (MOFs) is imperative and challenging for the development of practical MOF-based materials. Herein, a magnetically functionalized Zr-MOF (Fe3O4@MOF-525) was synthesized via secondary-growth approach to obtain an easily-separated and recyclable adsorbent for the removal of pharmaceuticals (tetracycline (TC) and diclofenac sodium (DF)). After loading Fe3O4 nanoparticles (NPs), due to the increase of micropore volume and specific surface area caused by defects, the adsorption performance of Fe3O4@MOF-525 was improved. The kinetics could be described by the pseudo-second-order kinetic model. The different adsorption capacity and initial rate were attributed to the properties of the pharmaceuticals, including the molecular size and hydrophobicity/hydrophilicity. In isotherm experiments, the maximum adsorption capacities of DF and TC on Fe3O4@MOF-525 calculated by Sips model reached 745 and 277 mg·g-1, respectively. The thermodynamic studies indicated the adsorption was endothermic and spontaneous. The effect of pH suggested that electrostatic interaction, π-π interaction, anion-π interaction, and H-bonding were possibly involved in the adsorption process. The adsorbent was separated by magnetic and regenerated. Washed with ethanol, Fe3O4@MOF-525 remained about 80% adsorption capacity after four cycles. In-situ photo-regeneration under visible-light irradiation was another attractive method, where > 95% TC was degraded in 4 h. The reaction with scavengers revealed that 1O2 was the dominant reactive species in our system, indicating the occurrence of Type II photosensitization. The separability, excellent adsorption performance, and recyclability of Fe3O4@MOF-525 may lead to its beneficial applications in water treatment.