Lee Yongjae, Kim Sun Jin, Bull Ivor, Celestian Aaron J, Parise John B, Kao Chi-Chang, Vogt Thomas
Department of Earth System Sciences, Yonsei University, Seoul 120-749, Korea.
J Am Chem Soc. 2007 Nov 7;129(44):13744-8. doi: 10.1021/ja075037z. Epub 2007 Oct 13.
A new potassium gallosilicate zeolite with a natrolite topology (approximate formula K8.2Ga8.2Si11.8O40.11.5H2O) was synthesized under hydrothermal conditions and characterized as a function of temperature using monochromatic synchrotron X-ray powder diffraction and Rietveld analyses. Unlike the previously known tetragonal K8Ga8Si12O40.6H2O phase, the as-synthesized material contains twice the amount of water molecules in an ordered arrangement throughout the channels in an orthorhombic (I212121) symmetry. The ordered configuration of water molecules is stabilized below 300 K, whereas heating above 300 K results in a selective dehydration and subsequent disordering of water molecules in a tetragonal (I2d) symmetry. Above 400 K, the material transforms to a fully dehydrated tetragonal phase with a concomitant volume reduction of ca. 15%. The fully dehydrated material transforms back to its original state when rehydrated over a period of up to 2 weeks. The distribution of potassium cations within the channels remains largely unperturbed during the water rearrangements and their order-disorder transition within the channels.
一种具有钠沸石拓扑结构的新型钾镓硅酸盐沸石(近似化学式为K8.2Ga8.2Si11.8O40·11.5H2O)在水热条件下合成,并使用单色同步加速器X射线粉末衍射和Rietveld分析对其作为温度函数进行了表征。与先前已知的四方相K8Ga8Si12O40·6H2O不同,合成后的材料在正交(I212121)对称结构的整个通道中含有两倍数量的水分子,且呈有序排列。水分子的有序构型在300 K以下稳定,而加热到300 K以上会导致选择性脱水,随后水分子在四方(I2d)对称结构中无序排列。在400 K以上,该材料转变为完全脱水的四方相,伴随体积约减少15%。完全脱水的材料在长达2周的时间内重新水化时会变回其原始状态。在水分子重排以及它们在通道内的有序 - 无序转变过程中,通道内钾阳离子的分布基本保持不变。