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Fe-containing ZSM-5 zeolite, or [Fe, Al]MFI, is known to catalyse various chemical reactions. Recently, it has gained increasing attention for its catalytic performance in the direct oxidation of benzene to phenol, using N2O as oxidant (BTOP). However, despite extensive efforts, the nature of the active sites in the [Fe, Al]MFI catalyst for the BTOP reaction is still largely unknown. This is mainly due to various synthesis and activation methods of [Fe, Al]MFI catalysts that have led to different interpretations. Nevertheless, there seems to be a consensus in open literature that steam-treatment of isomorphously substituted [Fe, Al]MFI zeolite forms a particular extra-framework iron species ...