DFT Study of Nitrogen-Substituted FAU: Effects of Ion Exchange and Aluminum Content on Base Strength

• Published in: Journal of physical chemistry. C 2011-01, Vol.115 (1), p.188-194
• Main Authors: Agarwal, Vishal, Conner, W. Curtis, Auerbach, Scott M
• Format: Article
• Language: English
• Subjects: C: Surfaces, Interfaces, Catalysis
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp106971u

We have studied base strengths of nitrogen-substituted (nitrided) zeolites with faujasite (FAU) structure by calculating sorption energies of probe molecules (BF3 and BH3) using density functional theory with mixed basis sets applied to embedded clusters. BH3 was found to be a better probe of base strength because it does not introduce competing metal−fluorine interactions that obfuscate trends. In all cases, the base strengths of nitrided zeolites (denoted M−N−Y) were found to exceed those of the corresponding standard M−Y zeolites, where M = Li, Na, K, Rb, or Cs charge-compensating cations. We have found that for a particular Si:Al ratio, BH3 sorption energies vary in the order Li < Na < K ∼ Rb ∼ Cs. Sorption energy and hence base strength was found to decrease with increasing Si:Al ratio from 1 to 3 beyond which the base strength was found to increase again. The initial regime (1 < Si:Al < 3) is consistent with the prevailing understanding that the base strength increases with Al content, while the latter regime (Si:Al > 3) involves the surprising prediction that the base strength can be relatively high for the more stable, high-silica zeolites. In particular, we found the sorption energy in Na−N−Y (Si:Al = 11) to be nearly equal to that in (Si:Al = 1). Taken together, these results suggest that K−N−Y (Si:Al = 11) optimizes the balance of activity, stability, and cost.