多酸d-f异金属微孔晶态材料的分步合成及催化降解制药废水的研究

The d-f heterometal porous compounds based on polyoxometalates are a special kind of crystal material. It can fuse the porous characteristics of MOFs and the catalytic properties of polyoxometalates and d-f heterometallic complexes together, which will be widely applied in the molecular catalysis field and so on. If the traditional "one pot" method is used, there exists intense coordination competition between d and f metals and large accidental factors. Thus it is difficult to control the final structures. Herein, in order to solve these problems on the assembly, we try to design and assemble this kind of materials by a stepwise assembly method. Firstly, we will preparate two kinds of precursors (d-f heterometal complexes and substituted/sandwich polyoxometalate). Then, two routes: “d-f heterometal precursor + polyoxometalates system” and “transition metal substituted/sandwich polyoxometalates + f metal complex system” will be used to obtain the d-f heterometal porous materials based on polyoxometalates. Furthermore, such materials will be fully characterized by spectroscopic analysis, mass spectrum, nuclear magnetic resonance and X-ray single crystal diffractions. And the properties of the materials on photocatalytic degradation of pharmaceutical wastewater will be studied systemically.

多酸基d-f异金属微孔化合物是一类特殊的晶态材料。此类材料复合了金属有机骨架化合物（MOFs）的多孔特点和多酸、d-f异金属材料的催化性能，将在分子催化等诸多领域具有广泛的应用前景。如果采用传统的“一锅法”制备该类化合物，将存在d和f金属之间配位竞争激烈，偶然因素大、最终结构不易控制等问题。为了解决组装上的困难，本项目拟采用分步组装策略：第一步，设计合成两种前驱体：①d-f异金属簇，②过渡金属取代/夹心型多酸；第二步，分别以“d-f异金属簇 + 多酸体系”和“过渡金属取代/夹心型多酸 + f金属配合物体系”两条路线，制备一系列多酸d-f异金属微孔材料，采用质谱、核磁和单晶衍射等方法表征其结构，并系统的研究其催化降解制药废水的催化性能。

本项目执行过程中，运用分步组装等技术，制备了新颖的多酸基d-f异金属微孔化合物及d/f金属修饰的多酸基化合物，运用元素分析、红外、热重分析和单晶衍射等多种检测技术系统表征了所制备材料的结构，深入研究了所制备材料的电化学、荧光及光催化等性质，进一步以有机污染物为模型分子，研究了其光催化性能，筛选性能优异的多酸基d-f异金属微孔化合物，考察了其光催化降解制药废水的催化性能，为此类材料的后续应用开发提供了实验基础与理论依据。在基金委的大力扶持与资助下，团队成员的共同努力下，本项目取得一些可喜的成果，累计发表SCI论文11篇，授权发明专利3项，培养硕士和博士研究生多人，项目成员获得了较好的发展，项目负责人入选黑龙江省普通本科高等学校青年创新人才培养计划。