Cluster model DFT calculations of CO adsorption on various possible forms of gallium in Ga/HZSM-5 zeolites have been performed. CO was found to only weakly interact with Ga + , (GaO) + , and (Ga(OH) 2-n H n ) + (n ) 1, 2) cationic clusters. The resulting shifts of the CO stretching frequency (∆ν CO ) are only very small. On the other hand, CO coordination to small mononuclear and binuclear Ga 3+ hydride/hydroxide/oxide species results in positive shifts in the stretching frequency in the range ∆ν CO ) 20-40 cm -1 . Larger shifts (∆ν CO ) 70-90 cm -1 ) are associated with CO coordination to Ga ions at the corners of small three-dimensional Ga-oxide clusters. The experimentally observed changes in the infrared spectrum of adsorbed CO over Ga/HZSM-5 zeolites upon reductive and oxidative treatments are interpreted with these insights. Possibilities for the formation of such polynuclear oxide species in the zeolite micropore space are discussed. On the basis of recent literature insights, we suggest that large shifts derive from CO coordination to oligomeric Ga cationic complexes stabilized by the negative zeolite charge.

No abstract

No abstract

No abstract

No abstract

No abstract

No abstract

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.