In situ X-ray diffraction study of cesium exchange in synthetic umbite.
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The exchange of Cs(+) into H(1.22)K(0.84)ZrSi(3)O(9)2.16H(2)O (umbite-(HK)) was followed in situ using time-resolved X-ray diffraction at the National Synchrotron Light Source. The umbite framework (space group P2(1)/c with cell dimensions of a = 7.2814(3) , b = 10.4201(4) , c = 13.4529(7) , and = 90.53(1)) consists of wollastonite-like silicate chains linked by isolated zirconia octahedra. Within umbite-(HK) there are two unique ion exchange sites in the tunnels running parallel to the a-axis. Exchange Site 1 is marked by 8 member-ring (MR) windows in the bc-plane and contains K(+) cations. Exchange Site 2 is marked by a larger 8-MR channel parallel to , and contains H(2)O molecules. The occupancy of the Cs(+) cations through these channels was modeled by Rietveld structure refinements of the diffraction data and demonstrated that there is a two-step exchange process. The incoming Cs(+) ions populated the larger 8-MR channel (Exchange Site 2) first and then migrated into the smaller 8-MR channel. During the exchange process a structural change occurs, transforming the exchanger from monoclinic P2(1)/c to orthorhombic P2(1)2(1)2(1). This structural change occurs when Cs(+) occupancy in the small cavity becomes greater than 0.50. The final in situ ion exchange diffraction pattern was refined to yield umbite-(CsK) with the molecular formula H(0.18)K(0.45)Cs(1.37)ZrSi(3)O(9)0.98H(2)O and possessing an orthorhombic unit cell with dimensions a = 10.6668(8) , b = 13.5821(11) , c = 7.3946(6) . Solid state (133)Cs MAS NMR showed there is only a slight difference between the two cavities electronically. Valence bond sums for the completely occupied Exchange Site 1 demonstrate that Cs-O bonds of up to 3.8 contribute to the coordination of the Cs(+) cation.
author list (cited authors)
Fewox, C. S., Clearfield, A., & Celestian, A. J.
complete list of authors
Fewox, Christopher S||Clearfield, Abraham||Celestian, Aaron J