Ammonia-Assisted Quadrupled-Yield ZIF-67 Derivation Enables Single Oxygen-Dominated Nonradical Oxidation for Enhanced Ciprofloxacin Degradation

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.