Acceleration of goethite-catalyzed Fenton-like oxidation of ofloxacin by biochar

Abstract

While carbon materials have been well studied to stimulate the homogeneous Fenton-like processes, little was known about their impacts on iron mineral-catalyzed heterogeneous Fenton-like reactions. Here, it was found that biochar prepared at 300 °C or 600 °C (BC300 or BC600) greatly stimulated the degradation of ofloxacin (OFX) in a goethite (Gt)-mediated Fenton-like system. In 4 h, while only 38.4 % and 48.4 % OFX were removed in Gt/H₂O₂ and BC600/H₂O₂ systems, the removal efficiency reached over 94.0 % in Gt/BC600/H₂O₂ system. And the pseudo-first-order rate constant of Gt/H₂O₂, BC600/H₂O₂ and Gt/BC600/H₂O₂ systems were 0.12, 0.16 and 0.72 h^-1, respectively, indicating the occurrence of synergistically catalytic degradation. •OH was identified as the major oxidant. Both the •OH yield and the H₂O₂ utilization efficiency of Gt/BC600/H₂O₂ system were higher than those of Gt/H₂O₂ and BC600/H₂O₂ systems. BC600 showed better stimulation effects than BC300. The persistent free radicals (PFRs) of BC could activate H₂O₂ and partly contribute to •OH production in the Gt/BC/H₂O₂ system. While BC could not directly reduce Fe(III) in Gt, it improved the cycling of Fe(III)/Fe(II) through complexing Fe(III) with its carboxyl group. Potential pathways were proposed for OFX degradation in the Gt/BC/H₂O₂ system.

Keywords: Fe(III)/Fe(II) cycling; Hydroxyl radical; Iron complexation; Persistent free radicals; Synergistic catalysis.