Catalytic ozonation mechanism over M1-N3C1 active sites

Abstract The structure-activity relationship in catalytic ozonation remains unclear, hindering the understanding of activity origins. Here, we report activity trends in catalytic ozonation using a series of single-atom catalysts with well-defined M 1 -N 3 C 1 (M: manganese, ferrum, cobalt, and nickel) active sites. The M 1 -N 3 C 1 units induce locally polarized M − C bonds to capture ozone molecules onto M atoms and serve as electron shuttles for catalytic ozonation, exhibiting excellent catalytic activities (at least 527 times higher than commercial manganese dioxide). The combined in situ characterization and theoretical calculations reveal single metal atom-dependent catalytic activity, with surface atomic oxygen reactivity identified as a descriptor for the structure-activity relationship in catalytic ozonation. Additionally, the dissociation barrier of surface peroxide species is proposed as a descriptor for the structure-activity relationship in ozone decomposition. These findings provide guidelines for designing high-performance catalytic ozonation catalysts and enhance the atomic-level mechanistic understanding of the integral control of ozone and methyl mercaptan.