Surface-Confined Pt–Ov–Mn Atomic Interfaces Promote Deep Benzene Mineralization through Coupled Electron Transfer and Lattice-Oxygen Activation

Abstract Single-atom catalysts are promising for VOC abatement, but their application is limited by the trade-off between the stability of isolated atoms and the redox activity. Herein, we report a surface-confined Pt–Ov–Mn atomic interface constructed within the outer layer of Mn2O3 via thermal self-reconstruction. Oxygen vacancies trap isolated Pt atoms and electronically connect them with neighboring Mn centers, forming a vacancy-rich interfacial active center. For benzene oxidation, Pt1/Mn2O3 achieved a specific reaction rate of 45.70 μmol gPt–1 s–1 at 140 °C, which is 3.8 and 11.2 times those of the Pt nanocluster and nanoparticle counterparts, respectively. The catalyst also exhibited excellent thermal stability and enhanced tolerance to SO2 poisoning. Mechanistic studies reveal that the Pt–Ov–Mn interface enables electron–lattice-oxygen coupling: interfacial Pt 5d–Mn 3d electronic interaction upshifts the Pt d-band center, strengthening benzene π adsorption and promoting C–H activation and ring opening, while adjacent oxygen vacancies accelerate lattice-oxygen migration and replenishment through a Mars–van Krevelen cycle. This coupled pathway suppresses the accumulation of partially oxidized intermediates and drives deep mineralization to CO2. These findings identify surface-layer atomic interfaces as designable active centers for developing robust SACs toward hazardous VOC control.