Insights into the novel application of Fe-MOFs in ultrasound-assisted heterogeneous Fenton system: Efficiency,kinetics and mechanism

In this work, as a new strategy, ultrasound/H₂O₂/MOF system was firstly applied by environmental-benign Fe-MOFs (MIL-53, MIL-88B and MIL-101) for tetracycline hydrochloride removal. The synthetic Fe-MOFs were characterized by XRD, FTIR, SEM, XPS, N₂ sorption-desorption isotherms and CO-FTIR. MIL-88B demonstrated the best catalytic performance because of its highest amount of Lewis acid sites. Influencing factors, contrast experiment, and corresponding dynamics were carried out to obtain the best experimental conditions and reaction system. Under optimal conditions ([Tetracycline hydrochloride] = 10 mg/L, [MIL-88B] = 0.3 g/L, [H₂O₂] = 44 mM, [ultrasound power] = 60 W, and pH = 5.0), the-first-order kinetic rate constant k was calculated to be 0.226 min⁻¹, higher than the simple combination of the ultrasound system (0.004) and MIL-88B/H₂O₂ system (0.163), indicating the importance of synergistic effect between ultrasound and Fenton reaction. EPR test and quenching experiment proved that ·OH is mainly responsible for tetracycline hydrochloride removal. The major reaction path is the adsorption and decomposition of H₂O₂ by coordinative unsaturated iron sites on Fe-MOF, but it is not the only path. The direct decomposition of H₂O₂ and the cavitation effect caused by ultrasound also contribute to the generation of OH.