Revealing the Generation of High-Valent Cobalt Species and Chlorine Dioxide in the Co₃O₄-Activated Chlorite Process: Insight into the Proton Enhancement Effect

A Co₃O₄-activated chlorite (Co₃O₄/chlorite) process was developed to enable the simultaneous generation of high-valent cobalt species [Co(IV)] and ClO₂ for efficient oxidation of organic contaminants. The formation of Co(IV) in the Co₃O₄/chlorite process was demonstrated through phenylmethyl sulfoxide (PMSO) probe and ¹⁸O-isotope-labeling tests. Both experiments and theoretical calculations revealed that chlorite activation involved oxygen atom transfer (OAT) during Co(IV) formation and proton-coupled electron transfer (PCET) in the Co(IV)-mediated ClO₂ generation. Protons not only promoted the generation of Co(IV) and ClO₂ by lowering the energy barrier but also strengthened the resistance of the Co₃O₄/chlorite process to coexisting anions, which we termed a proton enhancement effect. Although both Co(IV) and ClO₂ exhibited direct oxidation of contaminants, their contributions varied with pH changes. When pH increased from 3 to 5, the deprotonation of contaminants facilitated the electrophilic attack of ClO₂, while as pH increased from 5 to 8, Co(IV) gradually became the main contributor to contaminant degradation owing to its higher stability than ClO₂. Moreover, ClO₂^- was transformed into nontoxic Cl^- rather than ClO₃^- after the reaction, thus greatly reducing possible environmental risks. This work described a Co(IV)-involved chlorite activation process for efficient removal of organic contaminants, and a proton enhancement mechanism was revealed.