阳离子型金属有机框架材料去除99TcO4‾构效关系的理论研究

99TcO4‾的快速高效去除是核乏燃料后处理和放射性环境污染防控中的重点研究课题之一。99TcO4‾因其稳定性高、水溶性好、难络合等本征物理化学性质，以及乏燃料后处理场景中强酸、强辐射场、高浓度竞争阴离子等极端复杂环境，给99TcO4‾快速高效去除带来巨大挑战。阳离子型金属有机框架材料（cMOFs）兼具选择性好、动力学快、吸附容量大、耐辐照等优点，有望能够解决99TcO4‾快速高效去除所面临的困难和挑战。然而，cMOFs去除99TcO4‾未知的构效关系限制了cMOFs的进一步设计与优化。本项目基于实验数据建立合理的理论模型，运用量子化学计算和分子动力学模拟刻画相关动力学及热力学过程。最终在分子水平上构建cMOFs几何结构、物理化学性质、抗衡离子种类与99TcO4‾去除性能的构效关系，为cMOFs在乏燃料处理以及放射性污染环境防控中的实际应用提供理论基础。

The rapid and efficient removal of 99TcO4‾ is one of the most crucial research topics in the area of nuclear spent fuel reprocessing and prevention of radioactive contamination. To date, the removal of 99TcO4‾ remains a great challenge due to its high stability, water solubility, difficult complexity, and other inherent physicochemical properties. Besides, the removal efficiency is often further reduced by extremely complicated environments such as high acidity, strong radiation field, and the presence of a huge amount of competing anions in spent fuel reprocessing. It is thus desirable to develop a class of solid-phase adsorption materials with excellent sorption selectivity, fast kinetics, high uptake capacity, and good radiation resistance to solve these difficulties and challenges. The cationic metal-organic framework materials (cMOFs) are among the most promising candidates for applications in the rapid and efficient removal of 99TcO4‾. However, the structure-activity relationship between cMOFs and the 99TcO4‾ removal performance has not been clearly described yet, and this limits the further development and applications of cMOFs-based adsorption materials. The project will establish a reasonable theoretical model via investigations on the existing experimental data. The kinetic and thermodynamic processes interplay between 99TcO4‾, competing anions, and cMOFs would be given by performing molecular dynamics simulations and quantum chemistry calculations. Based on these results, the structure-activity relationship between the physicochemical properties of the cMOFs/counterion species and their 99TcO4‾ removal performance would be established at the molecular level. It can provide theoretical fundamentals for the practical applications of cMOFs in nuclear spent fuel reprocessing and prevention of radioactive contamination.