Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks.
Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks.
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DOI：
10.1021/jacs.7b08748
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发表时间：
2017-11-15
影响因子：
15
通讯作者：
Schröder M
中科院分区：
文献类型：
--
作者：
Zhang X;da Silva I;Godfrey HGW;Callear SK;Sapchenko SA;Cheng Y;Vitórica-Yrezábal I;Frogley MD;Cinque G;Tang CC;Giacobbe C;Dejoie C;Rudić S;Ramirez-Cuesta AJ;Denecke MA;Yang S;Schröder M
在核废料处理过程中，作为裂变产物的放射性碘会被释放出来。因此，可持续核能的广泛实施需要发展有效的碘储存，同时具有高容量、稳定性和更重要的储存密度（从而使系统体积最小化）。在这里，我们报道了一系列坚固的多孔金属有机材料MFM-300(M) （M = Al, Sc, Fe, in）对I2的高吸附。MFM-300（Sc）表现出完全可逆的I2吸收率为1.54 g g - 1，其结构在I2包合/去除后完全不受干扰。利用XPS、TGA-MS、高分辨率同步x射线衍射、对分布函数分析、拉曼光谱、太赫兹光谱和中子光谱，结合密度泛函数理论建模，直接观察和定量了这些宿主体内的客体I2分子的吸附、结合域和动力学。这些互补的技术揭示了在分子水平上对宿主i2和I2-I2结合相互作用的全面理解。MFM-300（Sc）中I2的初始结合位点I2I位于[ScO4(OH)2]部分的桥接羟基附近[I2I···H-O = 2.263(9) Å]，占用率为0.268。I2II位于相邻配体分子的两个苯基环之间[I2II···苯基环= 3.378(9)和4.228(5)Å]。I2II与羟基的距离为4.565(2)Å，占有率为0.208。值得注意的是，在高I2负载下，在晶体学分辨率下观察到I2分子在受限纳米孔洞内史无前例的自聚集成三螺旋链，导致I2分子的高效包装，MFM-300（Sc）中的I2存储密度为3.08 g cm-3。
During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I2 adsorption in a series of robust porous metal–organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g–1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host–I2 and I2–I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H–O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm–3 in MFM-300(Sc).
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DOI：
10.1107/s0907444905036693
发表时间：
2006-01-01
影响因子：
2.2
作者：
Evans, P
通讯作者：
Evans, P
影响因子：
4.6
作者：
He, Jun;Duan, Jingjing;Xu, Zhengtao
通讯作者：
Xu, Zhengtao
影响因子：
8.4
作者：
Brunet G;Safin DA;Aghaji MZ;Robeyns K;Korobkov I;Woo TK;Murugesu M
通讯作者：
Murugesu M
影响因子：
15
作者：
Subrahmanyam, Kota S.;Malliakas, Christos D.;Kanatzidis, Mercouri G.
通讯作者：
Kanatzidis, Mercouri G.
影响因子：
11.9
作者：
Geng, Tongmou;Zhu, Zongming;Wang, Yu
通讯作者：
Wang, Yu