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Developing catalysts with high efficiency and excellent interference tolerance for practical application remains a challenge in catalytic ozonation process. Herein, the surface Vo-rich catalyst was successfully prepared by lattice-doping Co into zinc ferrite spinel, which exhibited efficient mineralization of recalcitrant organic pollutants. The contaminants removal was mainly attributed to the nonradical-based oxygen species of surface atomic oxygen (*O) rather than traditional hydroxyl radical (· OH). The experiments and DFT calculation results revealed that Vo was the main active sites for adsorption of ozone and production of *O. The O-O in ozone was dissociated at Vo, trigging the formation of *O. In addition, the Vo-driven nonradical catalysis showed high resistance to the coexisting ions (200 mM Cl-, SO 4 2- and NO 3 -) and exhibited excellent performance for actual wastewater treatment. This work provides a novel strategy to regulate the oxidation pathways in catalytic ozonation process for efficient mineralization of pollutants in complicated water matrices. [Display omitted] • The oxidation pathway can be regulated by the introduction of Vo. • Vo acted as the main active sites for the adsorption and activation of ozone. • The nonradical species of *O played major role in pollutants removal. • The catalyst with enriched Vo exhibited efficient mineralization of ibuprofen. • Vo-driven nonradical catalysis showed high resistance to the coexisting ions. [ABSTRACT FROM AUTHOR]

[Display omitted] • Anchoring cobalt on sandwich-like 2D MXene shows synergistic effect on PAA activation. • Highly efficient degradation of 2,4-DCP is observed at neutral condition. • Ti 3 C 2 T x MXene substrate accelerates recycling of ≡ Co(III)/≡ Co(II). • Acetylperoxyl radical is primarily responsible for contaminant degradation. • The Co@MXenes/PAA process was unaffected by water matrices. A novel Co@MXenes catalyst with unique structure was prepared through randomly anchoring cobalt on 2D sandwich-like MXenes to activate peracetic acid (PAA) for water decontamination. Compared to the conventional Co 3 O 4 nanomaterial, the Co@MXenes catalyst exhibits superior performance for PAA activation under neutral condition. In-depth investigation revealed that the Ti 3 C 2 T x MXene substrate triggered the ≡ Co(III)/≡ Co(II) cycle, which greatly enhanced the activation of PAA. The XPS and ICP techniques further demonstrated that Co@MXenes was highly stable with extremely low cobalt ion leaching and hence a superior reusability was obtained. Moreover, acetylperoxyl radical (CH 3 CO 3 ) was identified as the primary radical species responsible for organic micropollutants degradation, exhibiting high selectivity towards contaminants containing electron-rich groups. The novel technology exhibited a high tolerance of Cl− and good performance in real wastewater treatment. This work provides a promising effective catalyst for PAA activation and will facilitate PAA application in wastewater decontamination. [ABSTRACT FROM AUTHOR]