A zeolite containing Fe and Al in the framework positions of an MFI structure was produced by hydrothermal synthesis. Subsequent thermal pretreatment caused the Fe to migrate from the lattice and become stabilized at cation-exchange sites associated with framework Ad atoms. The interactions of CH4, N2O, and methanol with this material were investigated by IR spectroscopy and temperature-programmed reactions methods. Upon exposure of thermally pretreated Fe/Al-MFI to methanol, the Bronsted acid protons and hydroxyl groups associated with Si and Fe reacted to form surface methoxy groups. Separate infrared features were observed for methoxy species bound to Si and Fe. Exposure of Fe/Al-MFI to CH4 and N2O above similar to448 K resulted in the formation of methoxy groups bound to both Fe and Si and the simultaneous loss of hydroxyl groups associated with both elements. The formation of methoxy groups was not observed on either Al-MFI or Fe-MFI, suggesting that the active sites in the oxidation of CH4 to methoxy species by N2O are extraframework Fe atoms associated with framework Al. The methoxy groups residing on the catalyst decomposed when the temperature was raised above 523 K and no methanol was observed in the products; however, when the methoxv groups reacted with H2O at 523 K, these groups were rapidly hydrolyzed to form methanol. For Fe/Al-MFI, small amounts of methanol were observed when CH4 and N2O reacted over Fe/Al-MFI at temperatures above 523 K, but the selectivity to this product was less than 2%, the majority of the CH4 undergoing combustion. (C) 2004 Published by Elsevier Inc.