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Abstract

High-valent metal species generated in peroxymonosulfate (PMS)-based Fenton-like processes are promising candidates for selective degradation of contaminants in water, the formation of which necessitates the cleavage of O-H and O-O bonds as well as efficient electron transfer. However, the high dissociation energy of O-H bond makes its cleavage quite challenging, largely hampering the selective generation of reactive oxygen species. Herein, an asymmetrical configuration characterized by a single cobalt atom coordinated with boron and nitrogen (CoB₁N<sub>3</sub) is established to offer a strong local electric field, upon which the cleavage of O-H bond is thermodynamically favoured via promoted coupled electron-proton transfer process, which serves an essential step to further allow O-O bond cleavage and efficient electron transfer. Accordingly, the selective formation of Co(IV) = O in single-atom Co/PMS system enables highly efficient removal performance towards various organic pollutants. The proposed strategy also holds true in other heteroatom doping system to configure asymmetric coordination, thus paving alternative pathways for specific reactive species conversion by rationalized design of catalysts at atomic level towards environmental applications and more.