Efficient removal of several estrogens in water by Fe-hydrochar composite and related interactive effect mechanism of H₂O₂ and iron with persistent free radicals from hydrochar of pinewood

Recently, hydrochar (HC) with existed persistent free radicals (PFRs) has attracted researches' attention for the potential application in heterogeneous Fenton-like reactions, but studies on the interactive effects of H₂O₂, iron, and HC in removal of organic pollutants are still limited. In this paper, magnetic iron (hydr)oxides immobilized hydrochar composite (Fe/HC) derived from hydrothermal carbon (HTC) of pinewood were synthesized and characterized. The interactive effects of H₂O₂, iron, and HC in the removal of several estrogens were systematically investigated to understand the removal performance and related mechanism, especially at a pH range close to natural water environment. Batch experiments results showed that estrogens could be efficiently removed over Fe/HC material under a wide pH range of 4-9. Based on the analysis of electron spin resonance, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, and electrochemical impedance spectroscopy, mechanism study indicated that the carbon-centered PFRs on the surface of hydrochar can act as electron donors, and transfer the electrons on adsorbed O₂ to generate O₂^- rapidly, while the addition of H₂O₂ enhanced the transmission ability of electron to produce OH_(ads) on the material surface. The iron and hydrochar components contributed to the desirable removal of estrogens via the synergistic effect between catalysis and adsorption. This study provides a promising application for the use of Fe/HC materials on remediation of pollution with trace estrogens in water environment.