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Calorimetric and IR-spectroscopic study of methanol adsorption on zeolites

Journal Article · · Journal of Colloid and Interface Science; (United States)
; ; ;  [1]
  1. Russian Academy of Sciences, Petersburg (Russian Federation). I.V. Grebenshchikov Inst. of Silicate Chemistry

The heats of CH[sub 3]OH adsorption on sodium faujasites and mordenites with different Si/Al ratios in the framework and on zeolites A, ZK-4, and ZK-5 were measured calorimetrically. The IR spectra of adsorbed CH[sub 3]OH were determined for the same zeolites. The decrease of cation concentration with increasing Si/Al ratio in the framework of faujasites, mordenites, and zeolites A and ZK-4 results in the decrease of CH[sub 3]OH adsorption heats for the broad coverage range and in weakening of the [nu][sub OH] disturbance for adsorbed CH[sub 3][sub OH]. For highly dealuminated faujasite, the OH vibrations in adsorbed CH[sub 3]OH are strongly perturbed due to intermolecular interactions even at small coverages. The adsorption heat is very low in this case. Sodium cations at 8-membered oxygen rings of zeolite ZK-5 are more tightly bonded to the framework and so they are less active adsorption centers for CH[sub 3]OH molecules as compared to the appropriate cations of zeolite Na-A. The step on the adsorption heat curve for CH[sub 3]OH on zeolite Na-A in the coverage interval from 3 to 5 molecules/unit cell corresponds to the transition of adsorbed molecules from the interactions with cations in 8-membered oxygen rings to those with cations in 6-rings. The second step at coverages about 6 molecules/unit cell results from the crystallographic nonidentity of adsorption complexes formed by CH[sub 3]OH molecules with cations at 4-rings for different uptakes. The acidic structural OH groups of decationated mordenite are involved in strong hydrogen bonds with adsorbed CH[sub 3]OH molecules or protonate them.

OSTI ID:
7169853
Journal Information:
Journal of Colloid and Interface Science; (United States), Journal Name: Journal of Colloid and Interface Science; (United States) Vol. 165:2; ISSN 0021-9797; ISSN JCISA5
Country of Publication:
United States
Language:
English