Activation of Hydrogen Peroxide by a Titanium Oxide-Supported Iron Catalyst: Evidence for Surface Fe(IV) and Its Selectivity

Iron immobilized on supports such as silica, alumina, titanium oxide, and zeolite can activate hydrogen peroxide (H₂O₂) into strong oxidants. However, the role of the support and the nature of the oxidants produced in this process remain elusive. This study investigated the activation of H₂O₂ by a TiO₂-supported catalyst (FeTi-ox). Characterizing the catalyst surface in situ using X-ray absorption spectroscopy (XAS), together with X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), revealed that the interaction between H₂O₂ and the TiO₂ phase played a key role in the H₂O₂ activation. This interaction generated a stable peroxo–titania Fe­(III)–Ti–OOH complex, which reacted further with H₂O to produce a surface oxidant, likely Fe­[IV]  O²⁺. The oxidant effectively degraded acetaminophen, even in the presence of chloride, bicarbonate, and organic matter. Unexpectedly, contaminant oxidation continued after the H₂O₂ in the solution was depleted, owing to the decomposition of Fe­(III)–Ti–OOH by water. In addition, the FeTi-ox catalyst effectively degraded acetaminophen over five testing cycles. Overall, new insights gained in this study may provide a basis for designing more effective catalysts for H₂O₂ activation.