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weak π-complexation. The π-complexation character of the interaction was subsequently confirmed by ab inito molecular orbital calculations using N2 and an Ag-X cluster model and was referred to as “weak chemisorption-assisted adsorption”.7 Hutson et al. have recently reported the synthesis of mixed Li/Ag X-type zeolite in which the addition of very small amounts of Ag and the proper dehydration conditions resulted in enhanced adsorptive characteristics and increased energetic heterogeneity as compared to those of the near fully exchanged Li+-zeolites.8 The performance for air separation by the best of these sorbents, containing, on average, only one Ag per unit cell, was compared to that of the near fully Li+-exchanged zeolite using a standard PSA cycle by numerical simulation. The results showed that the new sorbent provides a significantly higher (>10%) product throughput, at the same product purity and recovery, when compared to that of the near fully Li+-exchanged zeolite. Numerous attempts have been made to reduce transition metal ions in zeolites for the purpose of forming highly dispersed metallic clusters for use as catalysts. These attempts have typically been completed via treatment at elevated temperatures and/or in reducing atmospheres (e.g., sodium vapor, hydrogen gas, carbon monoxide gas). However, color changes upon vacuum dehydration of silver-exchanged A-type zeolites were found to be related to the formation of metallic clusters within the sodalite cage or the 6-prism of the zeolite.9,10,11 Using volumetric sorption techniques and temperature programmed desorption, Jacobs et al. were able to relate these color changes to an auto- reductive process involving framework oxygen.11 Autoreduction is the reduction of the transition metal ion and the oxidation of water or lattice oxygen; this has been observed 10PDF Image | PSA USING SUPERIOR ADSORBENTS
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