Rational Designs for Highly Proton-Conductive Metal-Organic Frameworks
Rational Designs for Highly Proton-Conductive Metal-Organic Frameworks
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DOI：
10.1021/ja9040016
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发表时间：
2009-07-29
影响因子：
15
通讯作者：
Kitagawa, Hiroshi
中科院分区：
文献类型：
--
作者：
Sadakiyo, Masaaki;Yamada, Teppei;Kitagawa, Hiroshi
合成了一种新型金属有机骨架（MOF）：（NH 4）（2）（adp）[Zn-2（ox）（3）]中心点3 H（2）O（1），并对其结构进行了测定。我们提出了三种合理的设计，将质子载体引入到MOFs中。最简单的方法是将它们直接作为抗衡离子如NH 4+、H3 O+和HSO 4-引入骨架的孔中（I型）。第二种是将酸基放在骨架上，质子由它们提供（II型）。第三种是将酸性分子引入空隙（III型）。1通过使用阴离子框架（I型）引入NH 4+离子和将己二酸的羧基端基置于蜂窝状空隙（III型）中，证明了两种概念的组合。1在环境温度下显示出10（-2）S cm（-1）的超质子电导率，与在燃料电池中实际使用的有机聚合物如Nafion相当。这是第一个在环境温度下表现出10（-2）S cm（-1）的超质子电导率的MOF的例子。
A novel metal-organic framework (MOF), (NH4)(2)(adp)[Zn-2(ox)(3)]center dot 3H(2)O (1) was synthesized and its structure was determined. We propose three types of rational design to introduce proton carriers into MOFs. The simplest method is to introduce them directly as counterions such as NH4+, H3O+, and HSO4- into the pores of frameworks (type I). The second is to put acid groups on frameworks, the protons being provided from them (type II). The third is to incorporate acidic molecules into voids (type III). 1 demonstrated a combination of two of the concepts by introducing NH4+ ions using the anionic framework (type I) and putting carboxyl end groups of adipic acid in a honeycomb-shaped void (type III). 1 showed a superprotonic conductivity of 10(-2) S cm(-1) at ambient temperature, comparable to organic polymers such as Nafion, which is in practical use in fuel cells. This is the first example of an MOF to exhibit a superprotonic conductivity of 10(-2) S cm(-1) at ambient temperature.