Ionic Covalent Organic Frameworks with Spiroborate Linkage
Ionic Covalent Organic Frameworks with Spiroborate Linkage
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DOI：
10.1002/anie.201509014
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发表时间：
2016-01-26
影响因子：
16.6
通讯作者：
Zhang, Wei
中科院分区：
文献类型：
--
作者：
Du, Ya;Yang, Haishen;Zhang, Wei
通过螺硼酸酯键的形成，构建了一种新型的离子共价有机骨架（ICOF），它含有sp（3）杂化的硼阴离子中心和可调的抗衡阳离子。这些ICOF表现出高达1259 m2 g-1的高BET表面积，并吸附大量的H-2（高达3.11 wt%，77 K，1 bar）和CH 4（高达4.62 wt%，273 K，1 bar）。重要的是，这些材料显示出良好的热稳定性和优异的耐水解性，在浸入水或碱性溶液中两天后几乎保持完整。ICOF中永久固定的离子中心的存在使得能够以3.05 × 10（-5）S cm（-1）的室温锂离子电导率和0.80 +/-0.02的平均Li+迁移数值来运输锂离子。因此，我们的方法提供了一个方便的路线，高度稳定的COF与离子键，这可能会作为替代能源，如H-2，CH 4的吸收剂，也作为固体锂电解质/下一代锂电池的隔板。
A novel type of ionic covalent organic framework (ICOF), which contains sp(3) hybridized boron anionic centers and tunable countercations, was constructed by formation of spiroborate linkages. These ICOFs exhibit high BET surface areas up to 1259 m(2) g(-1) and adsorb a significant amount of H-2 (up to 3.11 wt%, 77 K, 1 bar) and CH4 (up to 4.62 wt%, 273 K, 1 bar). Importantly, the materials show good thermal stabilities and excellent resistance to hydrolysis, remaining nearly intact when immersed in water or basic solution for two days. The presence of permanently immobilized ion centers in ICOFs enables the transportation of lithium ions with room-temperature lithium-ion conductivity of 3.05 x 10(-5) S cm(-1) and an average Li+ transference number value of 0.80 +/- 0.02. Our approach thus provides a convenient route to highly stable COFs with ionic linkages, which can potentially serve as absorbents for alternative energy sources such as H-2, CH4, and also as solid lithium electrolytes/separators for the next-generation lithium batteries.