Boosting peroxymonosulfate activation over partial Zn-substituted Co3O4 for florfenicol degradation: Insights into catalytic performance, degradation mechanism and routes

[Display omitted] •The Zn substituted Co3O4 catalysts were prepared and applied in PMS activation for florfenicol removal.•The Zn substitution induced electron rearrangement and promoted oxygen vacancies formation in Co3O4.•The Zn substituted Co3O4 (Zn0.03Co) exhibited superior florfenicol removal and higher reaction rate than Co3O4.•The florfenicol degradation is highly dependent on PMS/Zn0.03Co/florfenicol dosage, temperature and initial pH.•The degradation mechanism and routes were proposed combining LC-MS/MS and theoretical calculation results. Florfenicol (FLO) is a broad-spectrum halogenated antibiotic (containing F and Cl atoms), and the discharged FLO in wastewater exhibits potential biotoxicity. Peroxymonosulfate (PMS) activation can generate reactive oxygen species (ROSs) to realize efficient degradation of organic pollutants. Herein, Zn-substituted Co3O4 (ZnxCo) catalysts were prepared and applied in PMS activation for FLO degradation. The physicochemical properties were systematically studied by combining experiments and density functional theory (DFT) calculation. The Zn partial substitution induced electron rearrangement and promoted oxygen vacancy (OV) formation in Co3O4. Zn0.03Co catalyst exhibited superior FLO removal, achieving a higher reaction rate of 0.112 min−1 than Co3O4 (0.053 min−1). The FLO degradation was highly dependent on the factors of PMS/Zn0.03Co/FLO dosage, temperature, initial pH, and coexisting inorganic anions. The Zn0.03Co also displayed outstanding performance in PMS activation for degradation of various typical organic pollutants. Electron paramagnetic resonance (EPR) spectra and quenching experiments indicated that both radical species (·OH, SO4·-, and ·O2-) and nonradical species (1O2) contribute to FLO removal. The redox cycle of Co3+/Co2+ and OVs played an essential role in PMS activation. The electron structure of FLO and parameters of PMS adsorbed on ZnxCo were calculated. The longer length of CoO and OO bonds for the adsorbed PMS could enhance its activation to generate ROSs. The intermediates were detected, and five degradation pathways were proposed. The acute and chronic toxicities of intermediates suggested that the dechlorination process is important for the toxicity attenuation of FLO. This study clarified the performance enhancement mechanism of Zn substitution on FLO degradation by PMS activation using Co3O4 based catalyst, which favors the development of PMS-based advanced oxidation processes for wast