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Employing an Unsaturated Th 4+ Site in a Porous Thorium–Organic Framework for Kr/Xe Uptake and Separation
Author(s) -
Wang Yanlong,
Liu Wei,
Bai Zhuanling,
Zheng Tao,
Silver Mark A.,
Li Yuxiang,
Wang Yaxing,
Wang Xia,
Diwu Juan,
Chai Zhifang,
Wang Shuao
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802173
Subject(s) - lanthanide , thorium , actinide , chemistry , praseodymium , coordination number , molecule , metal organic framework , metal , coordination sphere , inorganic chemistry , crystallography , analytical chemistry (journal) , ion , materials science , crystal structure , adsorption , organic chemistry , uranium , metallurgy
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. Th 4+ in SCU‐11 is 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 Th 4+ 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 m 2 g −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 cm 3 g −1 , 0.77 mmol g −1 , 3.17 mmol g −1 , respectively, and a Xe/Kr selectivity of 5.7.