A reexamination of the adsorption of CO and nitriles on alkali-metal mordenites: characterization of multiple interactions

The low temperature adsorption of CO and the room temperature adsorption of propionitrile and ortho-toluonitrile on LiMOR, NaMOR, KMOR and CsMOR zeolites have been investigated by FT-IR spectroscopy. Two different CO species, both most probably located in the main channels coordinated on Na ions at IV and VI sites, have been observed. They are associated to a shift of the CO stretching to higher frequencies, as usual. However, together, more strongly bonded species associated to a slight shift of the CO stretching to a lower frequency are also observed. Similar species, with the CN stretching shifted upwards (weaker adsorption) and with the CN stretching shifted downwards (stronger adsorption) are also observed in the case of the interaction of propionitrile (PrN), a molecule that should enter the main channels, and in the case of the interaction of ortho-toluonitrile (o-TN), whose access to the main channels should be highly hindered. The data show that the species characterized by a stronger adsorption but a lower stretching frequency may form both in the main channels and at the external surface. Their formation is easier with the larger cations. These species are identified as "multiply bonded", possibly to two cations. The evidence for this new interaction, stronger than the usual one site-one molecule species, may change considerably the view of the adsorption chemistry of cationic zeolites, from localized simple sites to cooperative complex interactions.