Biomimetic Oxidation with Fe‐ZSM‐5 and H2O2? Identification of an Active, Extra‐Framework Binuclear Core and an FeIIIOOH Intermediate with Resonance‐Enhanced Raman Spectroscopy

Abstract Developing inorganic materials that can mimic nature’s ability to selectively oxidise inert CH bonds remains a topic of intense scientific research. In recent years, zeolitic materials containing Fe and/or Cu have been shown to be highly active, heterogeneous catalysts for the selective oxidation of alkanes (including methane), amongst a range of other related oxidation challenges. By using resonance‐enhanced Raman spectroscopy, we demonstrate that, following high‐temperature pre‐treatment (activation), Fe‐containing ZSM‐5 possesses an active binuclear core, and forms a key FeOOH intermediate upon activation with H 2 O 2 . Both factors are reminiscent of biological oxidation catalysts, and may account for the unique ability of this material to selectively oxidise methane to methanol at low temperature.