共有結合性有機骨格構造の設計と高速イオン伝導機能の開拓

共价有机骨架(COF)是一类独特的结晶型多孔有机聚合物，可以构建有序的一维介孔孔道，在吸附、催化、半导体、传感和超级电容器等领域具有广泛的应用前景。我将晶态H3PO4引入到稳定的TAPT-DMTP-COF的孔道中，制备了孔中不同含量的H3PO4@TAPT-DMTP-COF。值得注意的是，H3PO4@TAPT-DMTP-COF在160°C时具有高达10^-2 S cm-1的质子电导率。在此之前，我们团队已经成功地提出了晶体共价有机骨架的介孔孔道可以被设计成质子载体的概念，并且质子电导率比微孔和非孔聚合物高2-4个数量级。然后，我还利用孔表面工程方法设计合成了孔壁上带有聚电解质单元的COF，并以稳定的COF为前驱体。添加了OH-的COF具有较高的OH-导电性。在80℃时，氢氧离子沿有序链的电导率达到10^-4 S cm-1，比文献报道的多孔聚合物的电导率高4个数量级。氢氧化物离子的传导需要0.16 eV的低活化能，并通过氢网络中的质子跳跃机制发生。这些结果为设计负离子导电材料提供了一条新的途径。

Covalent organic frameworks (COFs) are a unique class of crystalline porous organic polymer that enables the construction of ordered one-dimensional mesoporous channels with a wide range of promising applications such as adsorption, catalysis, semiconductor, sensing and super capacitors.I introduced crystalline H3PO4 to the pores of a stable TAPT-DMTP-COF and produced H3PO4@TAPT-DMTP-COF with different contents of H3PO4 in the pores. Notably, the H3PO4@TAPT-DMTP-COF achieves an exceptional proton conductivity up to 10^-2 S cm^-1at 160 °C.Previously our group has been successfully developed the concept that the mesoporous channels of crystalline covalent organic frameworks can be designed to be the container of the proton carriers and the proton conductivity has been 2-4 orders of magnitude higher than those of microporous and nonporous polymers.Then I also designed and synthesized COFs with polyelectrolyte units on pore walls by using pore surface engineering method and stable COFs as a precursor. The OH--appended COFs exhibited high OH- conduction. The conductivity of hydroxide ions along the ordered chains reached to 10^-4 S cm^-1 at 80 °C in water, which are four orders of magnitude higher than those of porous polymers reported. The hydroxide ion conduction requires low activation energy of 0.16 eV and occurs via a mechanism of proton hopping in the hydrogen network. These results suggest a new way based on crystalline porous covalent organic frameworks for designing anion-conducting materials.