Time-Resolved Diffraction Studies of Ion Exchange: K+ and Na+ Exchange into (Al, Ge) Gismondine (GIS) Na24Al24Ge24O96·40H2O and K8Al8Ge8O32·8H2O

Time-resolved in situ synchrotron X-ray powder diffraction (XRPD) was used to study ion-exchange mechanisms and pathways in K+ and Na+ forms of an aluminogermanate with the zeolite gismondine topology (AlGe-GIS). The Na+ and K+ forms differ in their distribution of extraframework cations with the Na+ ions ordered in the C-centered monoclinic Na-AlGe-GIS of unit-cell dimensions a = 14.490(3) A, b = 9.3840(2) A, c = 23.530(5)A, and(beta)= 105.90(3) and K+ ions disordered in the I-centered monoclinic K-AlGe-GIS of unit-cell dimensions a = 10.311(2) A, b = 9.749(1) A, c = 10.238(1) A, and (beta)= 90.000(2). Rietveld structure refinements indicate K+ first occupies sites K2, K4, and K6 in the [01] channel of the Na-AlGe-GIS structure. After 10% ((plus_minus)2%) K+ exchange into the [01] channel, the I2/a unit cell forms and subsequent replacement of Na+ is consistent with site independent exchange along the [01] and [201] channels. Ion exchange proceeded to approximately 90% ((plus_minus)1%) substitution of K+ into Na-AlGe-GIS within the course of the experiment. However, in the reverse exchange of Na+ into the K-AlGe-GIS, an abrupt growth of Na-AlGe-GIS occurred at 4.5% ((plus_minus)3.5%) Na+ exchange and ended at 10% ((plus_minus)2.5%) Na+ exchange. Bond valence calculations demonstrate that K+ has a stronger interaction with framework O2- (0.423 v.u.) than Na+ (0.242 v.u.) and the valence matching principle shows that Na+ has a stronger affinity to interstitial H2O. These results imply that the AlGe-GIS structure has a preference for K+ as the charge-balancing extraframework cation.