Preparation, Crystal Structure, and Luminescence Properties of Zeolite LTA Containing Extraframework Tantalum(V), Tantalum(II), Thallium(I), and Chloride,The Journal of Physical Chemistry C

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Preparation, Crystal Structure, and Luminescence Properties of Zeolite LTA Containing Extraframework Tantalum(V), Tantalum(II), Thallium(I), and Chloride
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-05-31 00:00:00 , DOI: 10.1021/acs.jpcc.6b03943
Hyeon Seung Lim ₁ , Joon Young Kim ₁ , Nam Ho Heo ₁ , Karl Seff ₂

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For the first time pentapositive cations have been introduced into a zeolite at extraframework positions. Their presence was confirmed by single-crystal crystallography using synchrotron X-radiation and energy-dispersive X-ray analysis. It was prepared by the thallous ion exchange (TIE) method: fully dehydrated Tl₁₂-LTA was treated with 3.0 × 10⁴ Pa of TaCl₅(g) at 473 K. The crystal structure of the product, |Ta²⁺_0.123(TaCl₆Tl₃)²⁺_0.246Tl⁺_9.84|[Si_13.4Al_10.6O₄₈]-LTA, was refined in the space group Pm3̅m (a = 12.099(1) Å) with all unique data to the final error index R₁ = 0.044 for the 639 reflections for which F_o > 4σ(F_o). TIE did not occur. Instead some TaCl₅ molecules decomposed to TaCl₂ and Cl₂(g), and TaCl₂ reacted with additional TaCl₅ molecules to form Ta²⁺ and TaCl₆^–. Octahedral TaCl₆^– ions center about 24.6% of the large cavities. Each Cl^– ion bonds to a Tl⁺ ion in the plane of an 8-ring to form a TaCl₆Tl₃²⁺ continuum in the near-surface volume of the crystal. The Ta²⁺ ions, 0.123(3) per unit cell, lie opposite 6-rings in the large cavities. All Tl⁺ ions occupy well-established cation positions near 6- and 8-rings. The photoluminescence spectrum of this material is a broad emission band between 350 and 500 nm, peaking at 410 nm.

中文翻译：

含骨架（V），钽（II），T（I）和氯化物的沸石LTA的制备，晶体结构和发光性能

五元阳离子正第一次被引入到骨架外位置的沸石中。通过使用同步加速器X射线和能量色散X射线分析的单晶晶体学证实了它们的存在。它是通过th离子交换（TIE）方法制备的：在473 K下用3.0×10 ⁴ Pa的TaCl ₅（g）处理完全脱水的Tl ₁₂ -LTA 。产物的晶体结构| Ta ²⁺_0.123（ TaCl ₆ Tl ₃）²⁺_0.246 Tl ⁺_9.84 | [Si _13.4 Al _10.6 O ₄₈] -LTA，空间群中进行精制PM 3米（一个= 12.099（1）a）用所有唯一数据到最终误差指数- [R ₁ = 0.044的639个反射为其˚F _ø >4σ（˚F _Ò）。没有发生TIE。相反，一些TaCl ₅分子分解为TaCl ₂和Cl ₂（g），而TaCl ₂与另外的TaCl ₅分子反应形成Ta ²⁺和TaCl ₆^–。八面体TaCl ₆^–离子居中于大腔的约24.6％。各自为Cl ^-离子键合到一个铊⁺在8环平面离子以形成TACL ₆铊₃²⁺在晶体的近表面体积连续统一体。Ta ²⁺离子，每晶胞0.123（3），在大腔中与6环相对。所有的Tl ⁺离子都占据6环和8环附近公认的阳离子位置。该材料的光致发光光谱是在350至500 nm之间的宽发射带，在410 nm处达到峰值。

更新日期：2016-05-31

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