Mn−Fe Dual‐Metal Assemblages on Carbon‐Coated Al2O3 Spheres for Catalytic Ozonation Oxidation: Structure, Performance, and Reaction Mechanism

Catalysts with high catalytic activity and low production cost are important for industrial application of heterogeneous catalytic ozonation (HCO). In this study, we designed a carbon-coated aluminum oxide carrier (C-Al₂O₃) and reinforced it with Mn-Fe bimetal assemblages to prepare a high-performance catalyst Mn-Fe/C-Al₂O₃. The results showed that the carbon embedding significantly improved the abundance of surface oxygen functional groups, conductivity, and adsorption capacity of γ-Al₂O₃, while preserving its exceptional mechanical strength as a carrier. The prepared Mn-Fe/C-Al₂O₃ catalyst exhibited satisfactory catalytic ozonation activity and stability in the degradation of p-nitrophenol (PNP). Electron paramagnetic resonance (EPR) and quenching experiments reveal that radical ( ⋅ OH and ⋅ O₂ ⋅ ) and nonradical oxidation (¹O₂) dominated the PNP degradation process. Theoretical calculations corroborated that the anchored atomic Fe and Mn sites regulated the local electronic structure of the catalyst. This modulation effectively promoted the activation of O₃ molecules, resulting in the generation of atomic oxygen species (AOS) and reactive oxygen species (ROS). The economic analysis on Mn-Fe/C-Al₂O₃ revealed that it was a cost-competitive catalyst for HCO. This study not only deepens the understanding on the reaction mechanism of HCO with transition metal/carbon composite catalysts, also provides a high-performance and cost-competitive ozone catalyst for prospective application.