Methane dehydroaromatization under nonoxidative conditions over Mo/HZSM-5 catalysts: Identification and preparation of the Mo active species

Complete reduction of Mo species interacting strongly with a HZSM-5 zeolite support in methane is difficult, and the reduction product, MoC x O y , is a key active species in methane dehydroaromatization (MDA) under nonoxidative conditions. Pretreatment in H 2 at 623 K could lead to topotactic transformation of the Mo species from hexagonally close packing (hcp) to face-centered cubic (fcc) structures; the fcc MoC x O y species are more active and more stable than the hcp MoC x O y in MDA. After initial H 2 pretreatment at 623 K, followed by a CH 4-treatment, the Mo species on a MoO 3/HZSM-5 catalyst prepared by mechanical mixing was reduced and carburized to form fcc α-MoC 1− x species on the extra surface of the zeolite. Methane molecules activated by the α-MoC 1− x were converted mainly into carbon deposits instead of benzene. Both the most active Mo species and the neighboring Brönsted acid sites are essential in obtaining a perfect catalyst in the reaction of MDA.