多通道金属有机框架杂化材料的氢键网络构筑及质子传导性能研究
发布时间：2019-04-11 08:12
【摘要】：金属-有机框架(metal organic frameworks,MOFs)具有长程有序的结构、高度的可设计性,可用于构筑理想的氢键网络,因而在质子传导领域备受关注。目前,影响MOFs质子传导性能的因素主要有质子浓度、质子迁移率、质子跳跃位点等。受材料结构模型的限制,质子传输路径的轮廓对质子传导性能的影响还未被证实。一种理想的解决方案是在同一个MOF中构筑不同的质子传输路径。MIL-101包含两种不同尺寸的笼,它们在空间上有序排列,分别形成了两种轮廓的通道——Z字形和直线型。由于MIL-101的笼拥有大尺寸的可进入的窗口,因此可以通过引入客体分子人为地构筑氢键通路。Keggin型多金属氧酸盐H3PW12O40(HPW)具有独特的纳米尺寸、强的Br?nsted酸性、良好的稳定性和丰富的质子跳跃位点,是一种理想的选择。在这里,我们将HPW分别引入到MIL-101的两种笼内,获得了Z字形和直线型两种不同轮廓的氢键网络。测试结果表明,直线型氢键网络的质子传输速率是Z字型氢键网络的两倍之多,进一步表明直线型路径相比于Z字形路径更有利于快速的质子传输。这为设计基于MOFs的质子导体提供了除载体/质子浓度和迁移率以外的新的观点。此外,我们用柔性的胺分子对担载HPW的MIL-101进行后合成修饰,进一步提高其质子电导率至1.52×10-2 S cm-1在80℃100%RH下。
[Abstract]:Metal-organic frameworks,MOFs (MOF), with its long-range ordered structure and highly Designability, can be used to construct ideal hydrogen-bonded networks, so it has attracted much attention in the field of proton conduction. At present, proton concentration, proton mobility, proton jump sites and so on are the main factors that affect the proton conduction performance of MOFs. Limited by the material structure model, the influence of the profile of the proton transport path on the proton conduction performance has not been confirmed. One ideal solution is to construct different proton transport paths in the same MOF. Mil-101 consists of two different size cages, arranged in order in space, forming two channels of contour-Z-shaped and straight-line. Since the cage of MIL-101 has a large and accessible window, the hydrogen bond pathway can be constructed artificially by introducing guest molecules. Keggin type polyoxometalate H3PW12O40 (HPW) has unique nano-size and strong Br?nsted acidity. Good stability and rich proton jump sites are an ideal choice. In this paper, we introduce HPW into two kinds of cages of MIL-101, and obtain two kinds of H-bond networks with Z-shape and linear contour. The test results show that the proton transfer rate of the linear hydrogen-bond network is twice as much as that of the Z-shaped hydrogen-bond network, which further indicates that the linear path is more favorable to the rapid proton transport than the Z-shaped path. This provides a new point of view for the design of proton conductors based on MOFs in addition to carrier / proton concentration and mobility. In addition, we modified the MIL-101 loaded with HPW with flexible amine molecules and further improved the proton conductivity of MIL-101 to 1.52 脳 10? s cm-1 at 80 鈩，
本文编号：2456244
[Abstract]:Metal-organic frameworks,MOFs (MOF), with its long-range ordered structure and highly Designability, can be used to construct ideal hydrogen-bonded networks, so it has attracted much attention in the field of proton conduction. At present, proton concentration, proton mobility, proton jump sites and so on are the main factors that affect the proton conduction performance of MOFs. Limited by the material structure model, the influence of the profile of the proton transport path on the proton conduction performance has not been confirmed. One ideal solution is to construct different proton transport paths in the same MOF. Mil-101 consists of two different size cages, arranged in order in space, forming two channels of contour-Z-shaped and straight-line. Since the cage of MIL-101 has a large and accessible window, the hydrogen bond pathway can be constructed artificially by introducing guest molecules. Keggin type polyoxometalate H3PW12O40 (HPW) has unique nano-size and strong Br?nsted acidity. Good stability and rich proton jump sites are an ideal choice. In this paper, we introduce HPW into two kinds of cages of MIL-101, and obtain two kinds of H-bond networks with Z-shape and linear contour. The test results show that the proton transfer rate of the linear hydrogen-bond network is twice as much as that of the Z-shaped hydrogen-bond network, which further indicates that the linear path is more favorable to the rapid proton transport than the Z-shaped path. This provides a new point of view for the design of proton conductors based on MOFs in addition to carrier / proton concentration and mobility. In addition, we modified the MIL-101 loaded with HPW with flexible amine molecules and further improved the proton conductivity of MIL-101 to 1.52 脳 10? s cm-1 at 80 鈩，
本文编号：2456244
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