Fluorine-Coordination Facilitated Interfacial Hydrolysis Builds Dual Sites for Efficient H₂O₂ Homolysis on FeOF

Fenton reaction has been widely applied in wastewater treatment, however, the homolytic cleavage of hydrogen peroxide (H₂O₂) toward selective formation of hydroxyl radical (•OH) remains a key challenge. In this study, the FeOF catalyst was synthesised by introducing highly electronegative fluorine atoms to modulate the coordination environment of iron sites. The resulting O-Fe-F configuration significantly enhances surface hydrolytic hydroxylation, increasing the density of dual sites by 158% and achieving a breakthrough with 4.6-fold enhancement in •OH production. The generation of dual sites shifts the Fe d-band center upward toward the Fermi level (FeOCl: -3.403 → -3.014 eV; FeOF: -3.350 → -3.126 eV), reduces the rate-limiting energy barrier (FeOCl: 0.13 → -0.56 eV; FeOF: 0.11 → -0.88 eV), and the sites act as a bridge between FeOF and H₂O₂ to facilitate electron transport. Moreover, the FeOF-loaded in hollow fiber membrane demonstrates efficient pollutant removal and robust long-term stability in continuous operation of real water matrices with a flux up to 398 L m^-2 h^-1. This work offers a new theoretical framework for the design of efficient Fenton-like catalysts.