DRIFT study of methane adsorption by ZnZSM-5 zeolites prepared by incipient wetness impregnation or by chemical reaction of the initial hydrogen form with zinc vapor at 770 K indicated an unusually broad DRIFT band with a maximum at 2805 cm(-1). This frequency is more than 200 cm(-1) lower than the asymmetric nu(3) C-H stretching mode of gaseous methane and more than 100 cm(-1) lower than the symmetric nu(1) stretching frequency. Methane adsorption by zinc cations is much stronger than that by the bridging hydroxyl groups or sodium ions. At 473 K adsorbed methane is involved in heterolytic dissociation, resulting in formation of bridging hydroxyl groups and zinc alkyls. Such dissociative adsorption blocks the sites for subsequent molecular adsorption of methane or hydrogen. In accordance with our previous results on hydrogen adsorption, we conclude that the dissociative methane adsorption Occurs on acid-base pairs with distantly separated Zn2+ ions and basic oxygen atoms of the zeolite framework. Unusually large perturbation and dissociation of methane at the relatively low temperature are connected with only partial compensation of the positive electric charges of Zn2+ ions at such sites. (C) 2004 Elsevier Inc. All rights reserved.