Orbital‐Hybridization‐Driven N‐Fe‐Mo Interatomic Charge Bridges at Amorphous FeMoO _x /Porous Carbon Nitride Interface Boosting Peroxymonosulfate Activation in Fenton‐like Reaction

Peroxymonosulfate (PMS)-based Fenton-like reactions have emerged as a promising strategy for wastewater treatment. However, conventional catalysts are affected by the sluggish reduction rate of Fe (III) to Fe (II) and interfacial electron transfer with PMS. Herein, an orbital-hybridization strategy is proposed to construct directional N-Fe-Mo charge-transfer bridges across amorphous FeMoO_x and porous carbon nitride (pCN), thereby enabling ultrahigh PMS activation efficiency. The strong interfacial interaction of FeMoO_x with pCN induces orbital hybridization between the N 2p and Fe 3d orbitals, while simultaneously promoting electron redistribution between Fe and Mo centers. Different characterization methods, experimental verification, and theoretical calculations demonstrated that the unique N-Fe-Mo structures act as electron highways to accelerate PMS activation and reduce the energy barrier of the reaction, further generating highly selective singlet oxygen (¹O₂) as the main reactive oxygen species. A long-term continuous-flow experiment revealed >99% Rhodamine B (RhB) removal efficiency over 50 h of continuous operation, treating 75 L of wastewater. This work provides novel insights for designing atomic-scale charge-transfer bridges to enhance interfacial reactivity.