To enhance the contaminant removal efficiency of the electro-Fenton (E-Fenton) process, a nitrogen and phosphorus co-doped graphite felt (NPGF) cathode was synthesized using an anodic oxidation technique. An ascorbic acid-coupled NPGF E-Fenton system was then established for the degradation of ciprofloxacin (CIP). The NPGF cathode featured abundant oxygen-containing functional groups (such as -COOH and -OH), which enhanced the selectivity of oxygen reduction and facilitated the formation of H2O2. The introduction of N and P doping disrupted the charge balance within the carbon framework, accelerating electron transfer. Together, the NPGF electrode and ascorbic acid enhanced the cycling of Fe3+/Fe2+ while preventing the formation of iron sludge. Under optimal conditions (ascorbic acid concentration of 0.3 mM, current density of 2.0 mA cm-2, pH of 3.0, aeration rate of 0.6 L min-1, and Fe2+ concentration of 0.2 mM), CIP was completely removed within 20 min. The NPGF electrode exhibited excellent stability, maintaining 95.35% CIP removal even after 8 cycles. Analysis revealed that singlet oxygen primarily mediated the degradation of CIP, with its concentration measured at 1.23 × 10-7 M. Density functional theory was used to analyze the characteristics and potential attack sites of CIP, enabling the proposal of plausible degradation pathways. Toxicity simulations and Escherichia coli growth inhibition experiments demonstrated a reduction in the toxicity of CIP and its intermediate products. This study offers a valuable reference for improving the efficiency of E-Fenton technology in antibiotic wastewater treatment.
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