Enhanced catalytic performance of Cu-doped MnFe2O4 magnetic ferrites: Tetracycline hydrochloride attacked by superoxide radicals efficiently in a strong alkaline environment

Abstract

It is important to develop a catalyst that can maintain good activity in alkaline environment for Fenton or Fenton-like reactions. In order to achieve stable Fenton catalytic degradation in a wide pH range, this study reports Cu-doped MnFe₂O₄ heterogeneous catalysts still has excellent effect when the pH is extended to 11 for removing organic pollutants, such as tetracycline hydrochloride (TC-HCl). The synergistic effect among Fe, Mn and Cu ions has been proved to enhanced the catalytic activity in this work. When the molar ratio of Cu/Mn = 4:1, the porous Cu_0·8Mn_0·2Fe₂O₄ materials had the highest photo-Fenton catalytic activity compared with pure MnFe₂O₄, CuFe₂O₄ and other Cu_xMn_1-xFe₂O₄. The XPS showed that Cu_0·8Mn_0·2Fe₂O₄ formed oxygen vacancies, which exposed more active sites to attract more H₂O₂ for TC-HCl degradation. Results indicated 94.3% of TC-HCl was efficiently degraded by 0.1 g/L Cu_0·8Mn_0·2Fe₂O₄ with 50 mM H₂O₂ at pH = 11 under 30 min visible light irradiation, and the corresponding apparent rate constant was 0.08286 min^-1. With free radicals quenching experiment, O₂^- was responsible for the high catalytic degradation and OH was participated in the photo-Fenton reaction. To sum up, Cu_0·8Mn_0·2Fe₂O₄ exhibited high activity, great stability and easily recyclable, which eliminated the pH limitation of the Fenton reaction and provided practical application performance for water purification.

Keywords: Alkaline condition; Cu-doped MnFe(2)O(4); Heterogeneous photo-Fenton; Oxygen vacancies; Synergistic effect.