Overstepping Lowenstein's Rule-A Route to Unique Aluminophosphate Frameworks with Three-Dimensional Salt-Inclusion and Ion-Exchange Properties
Overstepping Lowenstein's Rule-A Route to Unique Aluminophosphate Frameworks with Three-Dimensional Salt-Inclusion and Ion-Exchange Properties
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DOI：
10.1021/acs.inorgchem.8b02906
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发表时间：
2019-01-07
影响因子：
4.6
通讯作者：
zur Loye, Hans-Conrad
中科院分区：
文献类型：
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作者：
Klepov, Vladislav V.;Juillerat, Christian A.;zur Loye, Hans-Conrad
合成了四种非洛文斯坦铀酰铝磷酸盐[Cs_（13）Cl_5][（UO_2）（3）Al_2 O（PO_4）（6）]、Rb-7[Al_2 O-（PO_4）（3）] [（UO_2）（6）O-4（PO_4）（2）]、Cs-3[Al_2 O（PO_4）（3）] [（UO_2）（3）O-2]和Rb-3[Al_2 O（PO_4）（3）][（UO_2）（3）O-2]。报道了第一种磷酸铀酰盐包合材料[Cs4 Cs4 Cl][（UO 2）（4）（PO 4）（5）]和相关结构的Cs-4[UO 2 Al 2（PO 4）（4）]，它们都是通过熔融熔剂法制备的。所有的化合物进行了讨论，从它们的结构特征的角度，有利于在某些情况下，离子交换性能。在沸石、铝硅酸盐和铝磷酸盐矿物领域中众所周知的洛温斯坦规则描述了通过氧桥连接的四面体（Al、P、Si和Ge）具有两种不同元素的趋势，导致避免Al-O-Al键。沸石和相关的铝硅酸盐/铝磷酸盐矿物传统上在相对温和的温度下形成，其中沸石使用水热合成技术合成。在磷酸铝中很少有例外，五种例外中有四种是在高温或高压下合成的。因此，四种新的非Lowenstein铀酰铝磷酸盐的高温熔剂合成实现了形成新的焦铝酸盐基结构单元[Al 2 O（PO 4）（6）]（14-）的独特合成方法，其可以容易地获得并用于构建新的多孔结构。
The synthesis of four non-Lowenstein uranyl aluminophosphates, [Cs13Cl5][(UO2)(3)Al2O(PO4)(6)], Rb-7[Al2O-(PO4)(3)] [(UO2)(6)O-4(PO4)(2)], Cs-3[Al2O(PO4)(3)] [(UO2)(3)O-2], and Rb-3[Al2O(PO4)(3)][(UO2)(3)O-2], the first uranyl phosphate salt-inclusion material [Cs4Cs4Cl][(UO2)(4)(PO4)(5)], and a related structure Cs-4[UO2Al2(PO4)(4)], all prepared by molten flux methods, is reported. All compounds are discussed from the point of view of their structural features favoring, in some cases, ion-exchange properties. Lowenstein's rule, well known in the realm of zeolites, aluminosilicate, and aluminophosphate minerals, describes the tendency of tetrahedra (Al, P, Si, and Ge) linked by an oxygen bridge to be of two different elements resulting in the avoidance of Al-O-Al bonds. Zeolites and related aluminosilicate/aluminophosphate minerals are traditionally formed under relatively mild temperatures, where zeolites are synthesized using the hydrothermal synthetic technique. Few exceptions to Lowenstein's rule are known among aluminophosphates, and four of the five exceptions are synthesized under either high temperature or high pressure methods. For that reason, the high-temperature flux synthesis of four new non Lowenstein uranyl aluminophosphates realizes a unique synthetic approach to forming the new pyroaluminate-based building block, [Al2O(PO4)(6)](14-), that can be easily obtained and employed for the construction of new porous structures.