Employing an Unsaturated Th4+ Site in a Porous Thorium-Organic Framework for Kr/Xe Uptake and Separation
Employing an Unsaturated Th4+ Site in a Porous Thorium-Organic Framework for Kr/Xe Uptake and Separation
复制标题
利用多孔钍有机框架中的不饱和 Th4 位点进行 Kr/Xe 吸收和分离
DOI：
10.1002/anie.201802173
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Wang Shuao
中科院分区：
文献类型：
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作者：
Wang Yanlong;Liu Wei;Bai Zhuanling;Zheng Tao;Silver Mark A.;Li Yuxiang;Wang Yaxing;Wang Xia;Diwu Juan;Chai Zhifang;Wang Shuao
基于榄系元素的金属-有机骨架(MOF)是独特的，不仅因为与过渡金属和稀土元素体系相比，它们被探索得更少，而且还因为鳗系元素离子在成键和配位方面的独特性。现在，3D钍有机骨架(SCU-11)包含一系列有效大小约为21×24 ä的笼子。在SCU-11分子筛中，Th~(4+)是10配位的双头四方棱柱配位几何构型，这在任何金属阳离子络合物中都从未见过报道。X-射线衍射、变色、热重和光谱分析证实，双折叠位置被两个配位的水分子占据，可以被移除以提供一个非常独特的开放的Th4+位。脱气相(SCU-11-A)的Brunauer-Emmett-Teller表面积为1272 m2g−1，是已报道的−材料中最高的值之一，使其能够充分保留水蒸气、Kr和Xe，其吸收容量分别为234cm3g−1、0.77 −1、3.17 g−1，Xe/Kr选择性为5.7。
Actinide based metal–organic frameworks (MOFs) are unique not only because compared to the transition‐metal and lanthanide systems they are substantially less explored, but also owing to the uniqueness of actinide ions in bonding and coordination. Now a 3D thorium–organic framework (SCU‐11) contains a series of cages with an effective size of ca. 21×24 Å. Th4+inSCU‐11is 10‐coordinate with a bicapped square prism coordination geometry, which has never been documented for any metal cation complexes. The bicapped position is occupied by two coordinated water molecules that can be removed to afford a very unique open Th4+site, confirmed by X‐ray diffraction, color change, thermogravimetry, and spectroscopy. The degassed phase (SCU‐11‐A) exhibits a Brunauer–Emmett–Teller surface area of 1272 m2g−1, one of the highest values among reported actinide materials, enabling it to sufficiently retain water vapor, Kr, and Xe with uptake capacities of 234 cm3g−1, 0.77 mmol g−1, 3.17 mmol g−1, respectively, and a Xe/Kr selectivity of 5.7.