具有可见光光催化性能的低聚金属卟啉直接键连多酸化合物的合成与密度泛函研究

A series of silicate ester and triatomic alcohol ligands with porphyrin oligomer fragment are designed, synthesized and grafted to several kinds of classical polyoxometalates (POMs) via condensation reaction to obtain novel organic-inorganic hybridized compounds with visible light catalytic activity. The photocatalytic degradation of organic dyes,electrochemical and other properties of these compounds will be investigated and their potential applications in the fields of photo catalysis will be explored. Based on density functional theory, the electronic structure of the central metal ions and the polymerization degree of metalloporphyrin(MP), and its grafting mode to POM will be studied to clarify their effects on the compositions of the molecular frontier orbitals and electron transition processes of the hybridized MP-POM compounds.The project helps to disclose the relathionship between the structure and photocatalytic behavior of the POM-based materials, and provides theoretical and experimental principles of POM applications.

本项目拟设计合成系列含低聚金属卟啉骨架的有机硅酸酯和三元醇类配体，通过缩合反应，与经典杂多酸盐前驱体嫁接，构筑基于低聚卟啉与杂多酸共价键桥连、具有可见光光催化活性的一维、二维有机-无机杂化化合物，考察其可见光光催化降解有机染料活性及电化学等性质，探索其在工业废水处理和光学材料等领域的潜在应用价值。采用密度泛函理论，探讨金属卟啉与杂多酸的嫁接模式、卟啉中心离子的电子结构、卟啉聚合度等因素对金属卟啉-多酸杂化物的轨道组成、电子跃迁特征等性质的影响，探讨其结构和功能之间的关系。项目的实施将有助于从分子水平理解聚合金属卟啉-多酸化合物的结构与其光催化性能之间的关系，为此类化合物作为新型可见光光催化剂提供实验和理论依据。

为拓展杂多酸在催化领域的基础应用，本课题以经典和非经典杂多酸为研究对象，采用密度泛函理论，以实验结合理论的方式，系统研究了经典与非经典Dawson型杂多酸的基本性质区别，建立了新型POM-I型杂多酸的分子力场模型及参数优化方案，并实现参数的自动程序优化。基于当前环境保护和可持续发展要求，开发了高活性的醇催化氧化双核铜簇合物绿色催化剂，多种新型黄光、荧光发光材料及环境污染物的监测和吸附的MOF材料。