Co-N3 site activated peroxymonosulfate for rapid degradation of ciprofloxacin: Synergistic effect of free radicals and nonfree radicals

Abstract

Nitrogen-doped metal-organic framework (MOFs)-derived carbon materials (denoted as Co-MOF-74@N-T-x) were successfully fabricated by calcinating Co-MOF-74, utilizing the green precursor of melamine. Among these materials, Co-MOF-74@N-500-2 demonstrated superior catalytic performance in activating peroxymonosulfate (PMS), achieving over 95 % degradation of ciprofloxacin (CIP) within 15 min, with a rate constant that was 1.25 times greater than that of Co-MOF-74-500. The primary active species identified in this study were sulfate radicals (SO4•−) and singlet oxygen (1O2), with the latter playing an important role in the degradation of CIP in the Co-MOF-74@N-500-2/PMS system. Theoretical calculations confirmed that the enhanced catalytic activity primarily stemmed from the Co-N3 configuration, which was more effective in activating PMS than the other configurations were. Co-MOF-74@N-500-2/PMS showed excellent performance in oxidizing CIP across a broad pH range (3.0–9.0) and demonstrated stability over five cycles, along with impressive degradation performance capabilities for a wide range of pollutants including metronidazole (MNZ), oxytetracycline (OTC), nitrofurantoin (FNT), methylene blue (MB), and acid orange (OG). This study presents a viable strategy for developing efficient and durable catalytic systems aimed at degrading organic pollutants via PMS.