Atomic-level Co/Mn tuning in bimetallic zeolites for reactive oxygen species pathway reconfiguration in peroxymonocarbonate activation

A Co Mn atomic switch reconstructs radical and non-radical PMC activation pathways. • Nominal waste O 2 is valorized into selective 1 O 2 via a unique cascade. • The non-radical route yields 13.3-fold rate hike and effluent detoxification. • High robustness is proven over 100-h continuous flow operation in real water matrices. Advanced oxidation processes (AOPs) hold great promise for pollutant abatement, yet selectively triggering non-radical pathways remains a formidable challenge, as radical and non-radical routes often compete kinetically. Here, by exploiting the confined framework of Silicalite-1 zeolites, we engineer bimetallic Co Mn sites where tailoring the Co/Mn ratio drives a structural evolution from isolated diatomic to nanoclusters, functioning as an atomic-scale switch to govern this competition in peroxymonocarbonate (PMC) activation. A Co-rich composition stabilizes atomically dispersed heteronuclear Co Mn sites featuring Mn-promoted Co(II) centers. This precise configuration kinetically inhibits direct peroxide cleavage and instead promotes interfacial single-electron transfer to oxygen (O 2 ), thereby valorizing this traditionally wasted byproduct into the non-radical singlet oxygen ( 1 O 2 ) generation. Conversely, a Mn-rich composition induces aggregated nanoclusters with abundant electron-deficient oxygen vacancies, which facilitate peroxy-bond dissociation and shift the reaction toward radical pathways. Corroborated by density functional theory and comprehensive experimental validations, this composition-dependent pathway regulation affords the optimized non-radical system a 13.3-fold kinetic enhancement and stable continuous-flow operation over 102 h. Download: Download high-res image (130KB) Download: Download full-size image