基于芳基对二甲酸的MOFs后功能化的过渡金属配合物催化有机膦降解的性能研究

Most organophosphorous (OPs) are the neurotoxins which can result in the direct or indirect toxic effect by inhibiting the neural sodium channel and acetylcholinesterase. Therefore, the design and development of the effective OPs degradation reagents under mild conditions is of great significance in the fields of the theory and application. Based on the previous work of the metallohydrolase mimics, this project will synthesize the composite systems of MOFs-complex for synergistic heterogeneous catalysis towards OPs degradation, in which the transition metal complexes as the active site are loaded on the metal-organic frameworks with the building block of p-aryl-formic acid by the post-synthetic method. The hydrolytic kinetics and catalytic intermediates of OPs degradation by the MOFs-complex will be studied in detail by the control of the factors, such as the post-synthetic functional complex types, quaternary ammonium groups, different MOFs, and pH values of reaction medium. The goals of this project are to explore the mechanism of OPs degradation catalyzed by MOFs-complex systems, and further reveal the relationship between the structure and activity. It will provide a new path for the treatment of waste water containing OPs pesticide residue.

有机膦化合物大多为神经毒素，抑制神经钠通道或乙酰胆碱酯酶，对人等非靶标生物会产生直接或间接毒性效应，设计和开发温和条件下高效的有机膦降解试剂具有重大的理论价值和广泛的应用前景。在前期水解酶模拟工作基础上，本项目拟采用芳基对二甲酸的金属有机框架化合物MOFs通过后合成的方法修饰过渡金属配合物，构筑MOFs-Complex复合体系，利用MOFs骨架的金属离子的路易斯酸性协同后修饰过渡金属配合物的催化活性位点，非均相催化有机膦毒物的磷氧键的水解断裂。通过调控后功能化的配合物及其季铵盐侧臂的种类、MOFs类型和催化介质的pH值等因素，系统研究MOFs-Complex复合体系催化有机膦降解的中间体结构和催化动力学，探索复合体系催化有机膦降解的机理，揭示其结构与催化活性的内在联系，为有机膦农药废水的污染治理提供新的应用途径。

利用高比表面的金属有机框架化合物MOFs进行均相催化剂的多相化，能有效解决均相催化剂的分离困难及不易重复使用和非均相催化剂的活性通常较差的问题。本项目以含芳基对二甲酸的MOFs为主要研究对象，在MOFs连接剂Linkers和其次级构筑单元SBUs修饰金属配合物，构筑了多种MOFs与配合物的复合体系作为催化有机膦降解的非均相催化剂。例如，联吡啶金属配合物修饰UiO-67体系、多联吡啶锌配合物修饰MIL-101(Cr)体系和一些其他过渡金属配合物修饰UiO-66-NH2和MOF-808等体系，研究了功能配合物类型、MOFs类型和形貌尺寸等因素对催化有机膦降解性能的影响。研究结果表明，多位点分离的MOFs复合体系中SBUs金属簇作为路易斯酸性位点和修饰配合物的金属-羟基作为路易斯碱性位点能协同高效催化有机膦中磷氧键的水解断裂，复合体系具有较高的循环稳定性。在本项目的资助下，我们还开展了一些探索性的工作，例如用于氨硼烷水解制氢和二氧化碳催化转化的催化剂的合成与性能研究等。