The widespread contamination of aquatic systems by ciprofloxacin (CIP)—a persistent fluoroquinolone antibiotic—poses severe ecological risks due to its antibacterial resistance induction. Conventional sulfate radical-based advanced oxidation processes (SR-AOPs) suffer from inefficient catalyst synthesis, exemplified by low-yield ZIF-67 precursors (typically <25%). To address this, a nitrogen-doped carbon composite Co₃O₄/N@C was synthesized via ammonia-assisted ligand exchange followed by pyrolysis, using N-doped ZIF-67 as a self-sacrificial template. The ammonia incorporation quadrupled precursor yield compared to ammonia-free methods. This catalyst activated peroxydisulfate (PDS) to degrade 95% CIP within 90 min under the optimized conditions (0.5 g/L catalyst, 2 mmol/L PDS, pH 5), representing a 30% enhancement over non-ammonia analogs. Mechanistic studies identified singlet oxygen (¹O₂) as the dominant reactive species, facilitated by N-doped carbon-mediated electron transfer. This strategy overcomes the scalability barrier of MOF-derived catalysts for practical antibiotic wastewater remediation.

Using norfloxacin (NOR) as the target pollutant, the synergism and degradation mechanism of ZnFe₂O₄-N-BC (MNBC), a nitrogen (N) and zinc ferrite (ZnFe₂O₄) co-doped biochar bifunctional catalyst (BC), in visible light (VIS)−peroxydisulfate (PDS) coupled system, were elucidated, and the synergistic mechanism was further supported by optical absorption and photo-induced charge transfer analyses. The results indicate that the degradation rate constant of the ZnFe₂O₄-N-BC/Vis-PDS system is 22.7 and 17.4 times higher than that of the ZnFe₂O₄-N-BC/Vis and ZnFe₂O₄-N-BC/PDS systems, respectively. More importantly, an apparent enhancement factor of 26.3% was obtained relative to the internal control systems. In addition, the coupled system showed a wider pH adaptation range. Furthermore, the radical quenching experiment and EPR analysis further revealed that multiple reactive species (including SO₄⁻, O₂⁻·, ·OH, h⁺, and ¹O₂) were involved in the degradation of NOR, and their relative contributions followed the order: ¹O₂ > SO₄⁻ > O₂⁻·> ·OH > h⁺. Finally, HPLC-MS analysis was performed to identify the key degradation intermediates of NOR, and thus to propose its possible transformation pathways.