Proton-gated multisite concerted proton-electron transfer-like pathway in a dual-atom framework for selective water purification.

Precise oxidant activation is essential for advanced water treatment but is often limited by radical quenching and low oxidant efficiency. Peroxymonosulfate (PMS) is promising; however, directing O-O cleavage towards non-radical pathways requires tightly coupled proton‒electron transfer, which is rarely achieved in heterogeneous catalysts because of spatially mismatched active sites. Here, we report a Co/Ni dual-single-atom metal-organic framework (MOF), in which atomically dispersed Co/Ni sites and adjacent noncoordinated -NH groups form a preorganized local microenvironment for PMS activation. Combined experimental and computational evidence suggests that Ni-assisted electronic coupling facilitates charge redistribution towards Co-bound PMS, while adjacent noncoordinated -NH motifs provide a local proton-relay environment, collectively favoring an MS-CPET-like pathway. This pathway promotes heterolytic O-O cleavage and the formation of a high-valent cobalt-oxo intermediate (Co(IV) = O). Consequently, the catalyst delivers a normalized rate constant of 6.2 × 10