Synergetic Manipulation Mechanism of Single-Atom M–N4 and M–OH (M = Mn, Fe, Co, Ni) Sites for Ozone Activation: Theoretical Prediction and Experimental Verification

Carbon-based single-atom catalysts (SACs) have been gradually introduced in heterogeneous catalytic ozonation (HCO), but the interface mechanism of O3 activation on the catalyst surface is still ambiguous, especially the effect of a surface hydroxyl group (M–OH) at metal sites. Herein, we combined theoretical calculations with experimental verifications to comprehensively investigate the O3 activation mechanisms on a series of conventional SAC structures with N-doped nanocarbon substrates (MN4–NCs, where M = Mn, Fe, Co, Ni). The synergetic manipulation effect of the metal atom and M–OH on O3 activation pathways was paid particular attention. O3 tends to directly interact with the metal atom on MnN4–NC, FeN4–NC, and NiN4–NC catalysts, among which MnN4–NC has the best catalytic activity for its relatively lower activation energy barrier of O3 (0.62 eV) and more active surface-adsorbed oxygen species (Oads). On the CoN4–NC catalyst, direct interaction of O3 with the metal site is energetically infeasible, but O3 can be activated to generate Oads or HO2 species from direct or indirect participation of M–OH sites. The experimental results showed that 90.7 and 82.3% of total organic carbon (TOC) was removed within 40 min during catalytic ozonation of p-hydroxybenzoic acid with MnN4–NC and CoN4–NC catalysts, respectively. Phosphate quenching, catalyst characterization, and EPR measurement further supported the theoretical prediction. This contribution provides fundamental insights into the O3 activation mechanism on SACs, and the methods and ideals could be helpful for future studies of environmental catalysis.