Revealing the Generation of High-Valent Cobalt Species and Chlorine Dioxide in the Co 3 O 4 -Activated Chlorite Process: Insight into the Proton Enhancement Effect.

A Co 3 O 4 -activated chlorite (Co 3 O 4 /chlorite) process was developed to enable the simultaneous generation of high-valent cobalt species [Co(IV)] and ClO 2 for efficient oxidation of organic contaminants. The formation of Co(IV) in the Co 3 O 4 /chlorite process was demonstrated through phenylmethyl sulfoxide (PMSO) probe and 18 O-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 ClO 2 generation. Protons not only promoted the generation of Co(IV) and ClO 2 by lowering the energy barrier but also strengthened the resistance of the Co 3 O 4 /chlorite process to coexisting anions, which we termed a proton enhancement effect. Although both Co(IV) and ClO 2 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 ClO 2 , while as pH increased from 5 to 8, Co(IV) gradually became the main contributor to contaminant degradation owing to its higher stability than ClO 2 . Moreover, ClO 2 - was transformed into nontoxic Cl - rather than ClO 3 - 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.