金属-有机多孔材料的设计与合成

In this proposal, we propose to synthesize multidentate organic ligands featured with linear, triangle, square, tetrahedral and other stereostructures. These ligands are proposed to synthesize porous metal-organic frameworks(Zr/Hf-MOFs) though the self-assembly with Zr/Hf metal cations under hydrothermal/solvothermal strategies. Several interesting explorations with respect to these porous Zr/Hf-MOFs will be carried out as followings: ⑴ The relationship between the MOFs structure and their physical/chemical properties; ⑵ The controlled synthesis of MOFs with special skeleton, porous structure and properties via tuning the organic spacers and self-assembly conditions; ⑶ The possibility to synthesize the composite via intaking issues by porous Zr/Hf MOFs and their properties; ⑷ Understanding in depth the influence of structure and outside conditions on the adsorption and catalysis properties as well as the relationship between the material structure and properties. The research in this proposal could give a chance to get further comprehension and meaningful theoretical support on such kinds of porous MOFs materials, and may promote the development of crystal engineering, controlling of material properties and material science theoretically and/or practically, which may provide useful insights to develop new porous MOFs.

本项目拟设计合成直线形、三角架形、正方形、四面体形等不同构型多齿配体，并研究其与锆/铪等金属离子通过水热/溶剂热等方法制备多孔锆/铪基金属-有机骨架材料（Zr/Hf-MOFs）。研究这些材料的结构和性质；探索有机链接的调控和制备条件的调控来调节骨架材料的结构、孔结构及材料的性质；并探索利用Zr/Hf-MOFs制备包合物及其性能；深入了解结构的变化以及外界因素的变化对材料的吸附性能和催化性能的影响，总结结构与性质之间的关系和规律。本项目的实施和完成将对这类多孔材料获得新的认识和理解，为这类材料的深入研究和可能的应用提供重要的理论基础和依据，并在晶体工程、材料性质的调控、材料科学等方面具有重要的理论和实际意义，为发展新型多孔材料提供一定的经验。

本项目采用水热及溶剂热的方法，利用含氮/不含氮的系列羧酸配体，辅以不同类型的小分子配体，和Co3+、Ni2+、Zn2+、Cd2+、Eu3+、Tb3+等过渡金属和稀土离子自组装合成了系列单核及异核的配位聚合物。同时研究了其结构，物理化学性能，以及潜在的应用。其中，以含有Co3+和Ni2+的大环配合物为前驱体制备的复合材料在作为电极材料，以及催化水产氢的研究中展现出较好的性能。本课题的实施和完成将对配位聚合物的深入研究和可能的应用提供一定的理论基础和技术依据，并在晶体工程、材料性质的调控、材料科学等方面具有重要的理论和实际意义，为发展新型多孔材料提供一定的经验。