99Tc是乏燃料后处理流程中最为棘手的放射性核素之一。由于Tc(VII)的氧化性，99TcO4−的存在会消耗PUREX流程中的还原剂，使铀钚分离下降，因此，在PUREX流程前，首先完成99TcO4−的分离对核燃料循环具有重要意义。本项以解决乏燃料后处理过程中99TcO4−的分离问题为导向，基于软硬酸碱理论，采用“硬硬结合”和“软软结合”两种策略，设计合成具有高酸稳定性的阳离子MOFs材料，并研究其在高酸度条件下对99TcO4−的吸附能力。系统研究金属中心配位构型、配体类型对目标阳离子框架结构酸稳定性的影响规律；借助单晶结构解析、理论计算等手段从微观角度精确阐释构效关系，以期获得具有潜在应用价值的阳离子MOFs材料。项目的实施有望实现耐酸型阳离子MOFs的设计合成，为新型99TcO4−吸附材料的构筑提供有益借鉴，同时为MOFs材料在实际乏燃料后处理中的应用提供研究基础和科研思路。

99Tc is one of the most problematic radionuclides in spent fuel reprocessing. Owing to the oxidation of Tc (VII), the presence of 99TcO4− could consume the reducing agents in PUREX process, thus leading to a reduction to the uranium-plutonium separation efficiency. Therefore, it is of great significance for the nuclear fuel cycle to separate 99TcO4− before PUREX process. Aiming at the separation of 99TcO4− in spent fuel reprocessing, and based on the hard and soft acids and bases theory (HSAB), the present project proposes two strategies, that are “combination between hard acids and hard bases” and “combination between soft acids and soft bases”, to design and synthesize cationic MOFs materials with excellent acid resistance, and investigate their 99TcO4− sorption capability under the condition of high acidity. The effects of coordination configurations of the meter centers and ligand types on acid stabilities of the final cationic frameworks will be systematically studied. The structure-function relationships will be precisely illuminated at the micro-scale by means of single crystal structure analyses and theoretical calculations, in order to gain cationic MOFs materials possessing great potential for applications. The project is expected to achieve the designed synthesis of acid resistant cationic MOFs, and provides useful references for the construction of novel 99TcO4− sorption materials, and also offer research foundation and scientific clues for the practical applications of MOFs in spent fuel reprocessing.