Peroxymonocarbonate activation via Co nanoparticles confined in metal-organic frameworks for efficient antibiotic degradation in different actual water matrices

Traditional advanced oxidation processes suffer from low availability of ultrashort lifetime radicals and declining stability of catalysts. Co nanoparticles in hollow bimetallic metal-organic frameworks (Co@MOFs) were synthesized via a solvothermal method. Nanoconfinement and peroxymonocarbonate (PMC) degradation system endows Co@MOFs with high catalytic activity and stability even in the actual water matrices. The nanocomposites exhibited 100-200 nm polyhedron structure with irregular nanocavity between the 20 nm shell and multicores. Co nanoparticles were completely encapsulated by the FeIII-MOF-5 shell according to the X-ray diffraction and photoelectron spectra. Both 0.8 nm micropores and 3.6 nm mesopores were proven to be present. The yolk-shell Co@MOFs exhibited higher catalytic performance than that of Co nanoparticles, hollow FeIII-MOF5 and its core-shell counterpart toward PMC activation during sulfamethoxazole degradation. The catalytic activities of Co@MOFs for the activation of unsymmetrical peroxides (PMC and peroxymonosulfate) were much higher than those for the symmetrical peroxides (H2O2 and persulfate) and the heterogeneous catalysis was dominant in the Co@MOFs activated H2O2 and PMC systems. The MOF stability was the highest and metal leakages were the least in the activated PMC system among the four peroxides because of mild reaction conditions and the alkalescent solution (pH = 8.3-8.4). Furthermore, the high removal efficiencies (>94%) and degradation rates could be maintained in the different actual water matrices due to the confinement effects. The contributions of carbonate and hydroxyl radicals were primary for sulfamethoxazole degradation, and superoxide anion and singlet oxygen also played essential roles according to scavenging experiments and time-series spin-trapping electron spin resonance spectra. Six degradation pathways were proposed according to 26 intermediate identification and the pharmacophores of more than 80% intermediates were destroyed, which would benefit subsequent biological treatment. Successful combination of nanoconfinement and PMC might provide a new effective solution for pollution remediation.