Peracetic acid catalytic activation using Co_(3)O_(4) nanocluster decorated graphitic carbon nitride for cefapirin degradation in water

This study innovated cobalt-based catalytic nanocomposites(CCNs)for the heterogeneous activation of peracetic acid(PAA),a green and efficient advanced oxidation process for removing antibiotics from water.Commercial Co_(3)O_(4) catalysts exhibit limited activity due to stable electronic structures.To overcome this,CCNs were synthesized using a one-step condensation method,incorporating a size control strategy that anchors Co_(3)O_(4) nanoclusters within 4‒5 nm onto six-fold cavity of g-C3N4,simultaneously modifying the coordination environment of Co.This alteration significantly enhances the adsorption energy of PAA and catalytic activity compared to commercial Co_(3)O_(4).The improved performance of CCN2,in particular,is attributed to a shift in the cobalt d band center towards the Fermi level,facilitating electron delocalization and transfer,enhancing Co‒O bonding,and accelerating PAA decomposition.CCN2’s superior activity,with a cefapirin(CFP)degradation kinetic rate constant(k1=0.760 min^(−1))~11 times that of PAA direct oxidation(k1=0.070 min^(−1))and~5 times that of commercial Co_(3)O_(4)/PAA system(k1=0.164 min^(−1)),is due to its ability to generate dominant reactive species for antibiotic degradation,including alkoxy radicals(CH3C(=O)OO•),high valence metal(Co^(Ⅳ)(=O)^(2+)),and singlet oxygen(^(1)O_(2)),with the latter two being crucial for the degradation process.The degradation of CFP involved three mechanisms,including direct oxidation by PAA,decarboxylation,and open-ring reactions at nitrogen sites.This research provides insights into developing high-activity catalysts for efficient PAA activation and antibiotic removal,leveraging the strategy of shifting the transition metal d band center.