Unveiling non-radical oxidation pathways in peroxymonosulfate/cobalt(II) systems: Critical role of cobalt(III) and cobalt(IV) explored by manganese(II) probing.

While non-radical Co species are recognized as critical intermediates in peroxymonosulfate (PMS)/Co(II) systems, their speciation and formation pathways remain under debate. In this study, Mn(II), characterized by well-defined redox behavior and mild reactivity toward radical species, was employed as a mechanistic probe to elucidate the activation mechanism of the PMS/Co(II) system under near-neutral conditions. Trace Co(II) (1 µM) accelerated Mn(II) oxidation kinetics by over 2000-fold at pH 8.0 compared to PMS alone. Scavenging experiments and near-100 % PMS utilization efficiency confirmed a non-radical mechanism. Co(IV) was proposed as the primary reactive species. Mn(III) capture experiments and density functional theory calculations indicated that Co(IV) oxidized Mn(II) via single-electron transfer. The derived Co(III) byproduct further contributed to Mn(II) oxidation, with reaction rates of 1.06 × 10⁵ M^-1·s^-1 at pH 5.5 and 1.20 × 10⁵ M^-1·s^-1 at pH 8.0. Kinetic modeling validated this pathway, quantifying the Co(IV)-Mn(II) reaction rates as 2.88 × 10⁶ M^-1·s^-1 (pH 5.5) and 2.57 × 10⁶ M^-1·s^-1 (pH 8.0). Under the experimental conditions, Co(III) and Co(IV) contributed comparably to Mn(II) oxidation. Mn(II)-probing experiments revealed that organic contaminant degradation was governed by substrate-dependent competition among three key reactive species: Co(II)-PMS complexes, high-valent cobalt species, and radicals. These findings provided mechanistic insights into PMS/Co(II) activation and further confirmed its potential for efficient manganese removal in water treatment.