Enhanced H2O2 utilization efficiency in Fenton-like system for degradation of emerging contaminants: Oxygen vacancy-mediated activation of O2

Abstract

Hydrogen peroxide (H₂O₂) is the most commonly used oxidant in advanced oxidation processes for emerging organic contaminant degradation. However, the activation of H₂O₂ to generate reactive oxygen species is always accompanied by O₂ generation resulting in H₂O₂ waste. Here, we prepare a Ti doped Mn₃O₄/Fe₃O₄ ternary catalyst (Ti-Mn₃O₄/Fe₃O₄) to create abundant oxygen vacancies (OVs), which yields electron delocalization impacts on enhancing the electrical conductivity, accelerating the activation of O₂ to produce H₂O₂. In Ti-Mn₃O₄/Fe₃O₄/H₂O₂ system, OVs-mediated O₂/O₂^•-/H₂O₂ redox cycles trigger the activation of locally generated O₂, boost the regeneration of O₂^•- and on site produce H₂O₂ for replenishment. This leads to a 100% removal of tiamulin in 30 min at an unprecedented H₂O₂ utilization efficiency of 96.0%, which is 24 folds higher than that with Fe₃O₄/H₂O₂. Importantly, further integration of Ti-Mn₃O₄/Fe₃O₄ catalysts into membrane filtration achieved high rejections of tiamulin (> 83.9%) from real surface water during a continuous 12-h operation, demonstrating broad pH adaptability, excellent catalytic stability and leaching resistance. This work demonstrates a feasible strategy for developing OVs-rich catalysts for improving H₂O₂ utilization efficiency via activation of locally generated oxygen during the Haber-Weiss reaction.

Keywords: Electron delocalization; H(2)O(2) generation; H(2)O(2) utilization efficiency; Oxygen activation; Oxygen vacancy.