Enhanced Kinetic Removal of Ciprofloxacin onto Metal-Organic Frameworks by Sonication, Process Optimization and Metal Leaching Study

Metal-organic frameworks (MOFs) are currently recognized as unique platforms for environmental studies. This study evaluated the potential of nine MOFs from ZIF-8, ZIF-67, and UIO-66 families for the removal of ciprofloxacin (CIP), a toxic, bio-accumulative, and persistent fluoroquinolone antibiotic. ZIF-67-SO(4), with a rhombic crystalline morphology and 1375 m(2)/g BET surface area, has the highest CIP adsorption efficiency among the studied MOFs. The mathematical sorption model predicted that the highest CIP removal (99.2%) occurs when adsorbent dose, pH, and agitation time are adjusted to 6.82, 832.4 mg/L, and 39.95 min, respectively. Further studies revealed that the CIP adsorbed onto ZIF-67-SO(4) in monolayer (q(max): 2537.5 mg/g) and chemisorption controlled the rate of the process. Mass transfer kinetic coefficients improved significantly by sonication at 35 KHz in comparison with mechanical agitation. Thermodynamic parameters (minus signs of ∆G° [7.8 to 14.2], positive signs of ∆H° (58.9 KJ/mol), and ∆S° (0.23 KJ/mol·K)) demonstrated the spontaneous, endothermic, and chemical sorption of CIP. The level of cobalt leached from ZIF-67-SO(4) structure varied 1.2–4.5 mg/L, depending on pH, mixing time, and agitation type. In conclusion, the excellent adsorption properties of ZIF-67-SO(4) for CIP, made it an outstanding candidate for environmental protection purposes.