Catalytic dehydroaromatization of methane has been investigated over 2-6 wt.% Fe-modified HZSM-5 or HMCM-22 zeolite in the absence of an added oxidant. After pretreatment in a CH4/Ar/He mixture, Fe/HMCM-22, and more significantly, Fe/HZSM-5 exhibited high catalytic activity in nonoxidative conversion of methane to aromatic hydrocarbons. This conversion actually takes part in three consecutive steps, oxidation of methane by iron oxides, decomposition, and aromatization of methane. During this conversion, XPS and XRD results showed the gradual reduction of Fe2O3 to metallic Fe, followed by the carburization of the metallic species. The fact that no aromatic products were detected until iron carbide was formed demonstrated that carburized Fe was the active species for the aromatization of methane. Under the same reaction conditions, both metallic Fe and carburized Fe were highly effective for activation of methane, but they catalyzed dehydrogenation of methane to carbonaceous materials and to aromatics, respectively. Difference in the catalytic properties of those two Fe species suggested that carburized Fe could stabilize carbene, the primary intermediate of activated methane, possibly via formation of a metal-carbene complex, C-Fe=CH2, so that carbene was able to dimerize into ethylene, which was then oligomerized to aromatics on the acid sites of the zeolite. (C) 2016 Elsevier Inc. All rights reserved.