Crystal Structure of Dehydrated CsZSM-5 (5.8Al): Evidence for Nonrandom Aluminum Distribution†

The crystal structure of dehydrated Cs5.8Al5.8Si90.2O192 has been determined by Rietveld refinement of synchrotron powder diffraction data. The structure was refined in the Pnma space group to Rwp = 2.52% and R(F2) = 5.32%. Cs ions were found with partial occupancy in three different positions. One of these, Cs1, is in the channel intersection, near the sinusoidal channel 10-ring system and adjacent to a four-membered ring. The second, Cs2, is in the straight channel 10-ring. The third, Cs3, is 3.18 A from the Cs1 and also in the sinusoidal channel 10-ring area. The total Cs occupancy is 5.32(3) Cs ions, which compares well with the Cs unit cell content of 5.8 calculated from the chemical analysis. Modeling of the effect of aluminum siting on the position of Cs+ ions in the zeolite channel indicates that the Cs+ ion has its closest interaction with an oxygen atom attached to the aluminum atom for Al substitution at each of the 12 ZSM-5 T-sites. From this result we conclude that Cs+ ion positioning provide...