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

共价有机框架（COFs）是一类独特的晶体多孔有机聚合物，能够构建有序的一维介孔通道，具有广泛的应用前景，如吸附、催化、半导体、传感和超级电容器。我将结晶H3PO4引入到稳定的tpt - dtmp - cof的孔隙中，得到了孔隙中H3PO4含量不同的H3PO4@TAPT-DMTP-COF。值得注意的是，H3PO4@TAPT-DMTP-COF在160°C下实现了高达10^-2 S cm^-1的优异质子电导率。在此之前，我们的团队已经成功地开发了一个概念，即晶体共价有机框架的介孔通道可以被设计成质子载体的容器，并且质子电导率比微孔和无孔聚合物高2-4个数量级。然后，采用孔表面工程的方法，以稳定的COFs为前驱体，设计并合成了孔壁上有聚电解质单元的COFs。OH-附加的COFs表现出高的OH-传导。氢氧根离子在水中80℃时沿有序链的电导率可达10^-4 S cm^-1，比已有报道的多孔聚合物的电导率高4个数量级。氢氧根离子的传导需要0.16 eV的低活化能，并通过氢网络中的质子跳变机制进行。这些结果为设计阴离子导电材料提供了一种基于晶体多孔共价有机框架的新途径。

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.