双配体调控的多酸基微孔晶态材料的制备与性能研究

Polyoxometalate-based microporous crystal materials are a special kind of composite function materials. It can fuse the porous characteristics of MOFs (Metal-organic frameworks) as well as the catalysis properties of POMs (polyoxometalates) together, which have wide applications, such as gas adsorption and molecular catalysis. To date, the synthesis routes of the POM-based microporous hybrid materials are all dependent on the synergic reaction of POM, metal and a single ligand. However, the charge, coordination mode and space configuration of a single ligand are relatively fixed, generally it can not obtain porous hybrid materials, and the number of the POM-based microporous crystal materials that reported in literature is very limited. Herein, we try to design and assemble a series of POM-based microporous crystal materials controlled by two-ligands. Based on the idea of molecular design, using the key merits of both components of two-ligands, we tune the charge, coordination mode and space configuration of the secondary ligand in order to obtain the porous materials. And thus, the catalytic properties of POM-based microporous crystal materials that we obtained can be enhanced. Furthermore, the basic physical properties of fluorescence and electrochemistry will be investigated in details. Also the gas adsorptions and catalysis properties will be studied. In all, this study will solve the "effective immobilization technology" problem of catalytic application of POMs and further extend the applications of POMs in material chemistry, molecular catalysis and so on.

多酸基微孔晶态材料是一类特殊的复合型功能材料，这类材料将金属-有机框架的多孔性与多酸优异的催化性能有机地结合起来，在气体吸附及分子催化等领域显示了巨大的应用潜力。目前鲜有报道的多酸基微孔杂化材料均局限于利用单一配体与多酸、金属离子之间的协同反应进行制备，但是由于单一配体的电荷、配位方式和空间构型相对固定，往往最终所得的材料并不具有孔结构，因此多酸基微孔晶态材料的制备和催化应用研究仍是一个极具挑战性的课题。本项目拟创新性地将双配体引入到制备反应体系中，制备一系列由双配体构筑的多酸基微孔晶态材料，并基于分子设计思想，通过调节主次级配体的电荷、配位模式和空间构型，调控晶态材料的微孔结构和尺寸，从而获得催化性能更加优异的多酸基微孔复合型晶态材料。同时，本项目将系统研究所制备材料的催化性能，解决多酸催化应用中“有效固载化”的技术难题，扩展多酸在材料化学以及分子催化领域的应用。

制备了包括首例双配体构筑的多酸基纳米管材料和首例囊包Keggin型多酸金属-有机纳米银笼材料等多种新颖的多酸基材料。并对所制备材料的电催化光解水制氢、光催化电解水制氢、电化学传感生物小分子等性能进行了系统的研究。研究结果表明所制备的材料具有优异的光电催化及电化学传感等性能，并揭示了多酸基材料的结构、组成和形貌等特性与其光电功能性质间的紧密联系规律。解决了传统多酸催化剂材料在应用过程中的“有效固载化”，传统多酸及金属氧化物电极材料稳定与导电性差等行业技术难题。本项目的实施为新型多酸及功能金属氧化物材料的设计制备及此类材料在催化、光/电/磁功能转化等方面的应用提供了理论指导与实验基础。此外， 本项目组累计发表SCI论文42篇；授权发明专利6件；培养研究生16人(博士生5人、硕士生11人；参加学术会议6次。