Integration of Intrinsic Proton Conduction and Guest-Accessible Nanospace into a Coordination Polymer
Integration of Intrinsic Proton Conduction and Guest-Accessible Nanospace into a Coordination Polymer
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DOI：
10.1021/ja4051668
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发表时间：
2013-07-31
影响因子：
15
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
--
作者：
Umeyama, Daiki;Horike, Satoshi;Kitagawa, Susumu
我们报道了一种既具有本征质子导电性又具有气体吸附性能的配位聚合物的合成和表征。由锌离子、苯并咪唑和正磷酸盐组成的配位聚合物表现出一定程度的柔韧性，因为它在脱水前后采用不同的结构。结果表明，脱水后的骨架具有较高的本征质子电导率，在120℃时可达1.3×10~(-3)S cm~(-1)。我们发现，苯并咪唑分子在骨架通道中的重排传导路径和类液体行为使其具有较高的质子电导率。在这两种形式的骨架中，只有脱水形式对甲醇是多孔的，并在结构中展示了客人可进入的空间。由于甲醇分子的原位吸附，脱水形式的质子电导率增加了24倍，表明了骨架的双重功能。核磁共振研究揭示了骨架与甲醇之间的氢键相互作用，这使得骨架内的质子电导率得以调节。
We report the synthesis and characterization of a coordination polymer that exhibits both intrinsic proton conductivity and gas adsorption. The coordination polymer, consisting of zinc ions, benzimidazole, and orthophosphate, exhibits a degree of flexibility in that it adopts different structures before and after dehydration. The dehydrated form shows higher intrinsic proton conductivity than the original form, reaching as high as 1.3 x 10(-3) S cm(-1) at 120 degrees C. We found that the rearranged conduction path and liquid-like behavior of benzimidazole molecules in the channel of the framework afforded the high proton conductivity. Of the two forms of the framework, only the dehydrated form is porous to methanol and demonstrates guest-accessible space in the structure. The proton conductivity of the dehydrated form increases by 24 times as a result of the in situ adsorption of methanol molecules, demonstrating the dual functionality of the framework. NMR studies revealed a hydrogen-bond interaction between the framework and methanol, which enables the modulation of proton conductivity within the framework.