Oxygen Vacancy Promoted Heterogeneous Fenton-like Degradation of Ofloxacin at pH 3.2–9.0 by Cu Substituted Magnetic Fe₃O₄@FeOOH Nanocomposite

Abstract

To develop an ultraefficient and reusable heterogeneous Fenton-like catalyst at a wide working pH range is a great challenge for its application in practical water treatment. We report an oxygen vacancy promoted heterogeneous Fenton-like reaction mechanism and an unprecedented ofloxacin (OFX) degradation efficiency of Cu doped Fe₃O₄@FeOOH magnetic nanocomposite. Without the aid of external energy, OFX was always completely removed within 30 min at pH 3.2-9.0. Compared with Fe₃O₄@FeOOH, the pseudo-first-order reaction constant was enhanced by 10 times due to Cu substitution (9.04/h vs 0.94/h). Based on the X-ray photoelectron spectroscopy (XPS), Raman analysis, and the investigation of H₂O₂ decomposition, ^•OH generation, pH effect on OFX removal and H₂O₂ utilization efficiency, the new formed oxygen vacancy from in situ Fe substitution by Cu rather than promoted Fe³⁺/Fe²⁺ cycle was responsible for the ultraefficiency of Cu doped Fe₃O₄@FeOOH at neutral and even alkaline pHs. Moreover, the catalyst had an excellent long-term stability and could be easily recovered by magnetic separation, which would not cause secondary pollution to treated water.