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

ABSTRACT 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 ( 1 O 2 ) 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.