Sulfonate-Functionalized Polyoxovanadate-Based Metal-Organic Polyhedra for Enhanced Proton Conduction via the Synergy of Linker and Metal Cluster Vertex
Sulfonate-Functionalized Polyoxovanadate-Based Metal-Organic Polyhedra for Enhanced Proton Conduction via the Synergy of Linker and Metal Cluster Vertex
复制标题
磺酸盐官能化多钒酸盐基金属有机多面体通过连接基和金属簇顶点的协同作用增强质子传导
DOI：
10.14102/j.cnki.0254-5861.2022-0127
复制
发表时间：
2022
影响因子：
2.2
通讯作者：
Xuan Weimin
中科院分区：
文献类型：
--
作者：
Zhang Yu;Liu Shanshan;Li Bo;You Hanqi;Zhang Longxi;Zhang Zhenyi;Zang Hongying;Zheng Qi;Xuan Weimin
金属有机多面体（MOPs）是一种新型的质子导电多孔平台，然而，将连接体和金属簇顶点结合起来制备MOPs基高导电材料的研究还很少。在本文中，我们报道了磺酸盐官能化的基于多钒酸盐的MOPs的合成，用于通过连接体和金属簇节点的协同效应来增强质子传导。MOPs 1和MOPs 2具有由{V_5O_9Cl}顶点和5-磺酸基连接基团构成的八面体笼状构型。由于八面体笼沿着三个轴的有序堆积，因此在2.与质子传导{V5 O 9 Cl}顶点以及质子化抗衡离子耦合，因此产生了广泛的氢键网络，用于容易的质子转移。在65 °C和90%RH条件下，2的质子电导率为3.02×10~（-2）S cm~（-1），是MOPs样品中最高的。与羧酸酯官能化的类似物3相比，该值提高了约1个数量级，清楚地说明了将连接体和金属簇节点组合用于增强质子传导的优点。本文的工作将进一步推动高质子传导MOPs基材料的协同设计策略的开发。
Metal-organic polyhedra (MOPs) have emerged as novel porous platforms for proton conduction, however, the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials. Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node. MOPs 1 and 2 exhibit octahedral cage configuration constructed from {V_5O_9Cl} vertex and 5-sulfoisophthalate linker. Owing to the ordered packing of octahedral cages along three axes, 3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2. Coupled with the proton-conductive {V5O9Cl} vertexs as well as protonated counterions, an extensive H-bonded network is therefore generated for facile proton transfer. 2 exhibits high proton conductivity of 3.02×10~(-2) S cm~(-1) at 65 °C under 90% RH, recording the highest value for MOPs pellet sample. This value is enhanced ~1 order of magnitude compared with that of carboxylate-functionalized analogue 3, clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction. This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.