多孔材料用于废水中放射性核素吸附的研究进展

doi:10.16085/j.issn.1000-6613.2024-0095

摘要/Abstract

摘要：

针对传统吸附剂对放射性元素的去除，存在吸附时间较长以及吸附效果不理想等不足之处；新型多孔吸附材料如共价有机框架（COF）、金属有机框架（MOF）和共轭微孔聚合物（CMP）等，由于优异的物理化学特性，高比表面积、高孔隙率、快速的电荷载流子迁移率和可调的功能性，对于放射性核素的分离有着更高的分离效率。本文针对多种新型多孔吸附材料COF、MOF和超高交联聚合物（HCP）等对放射性元素的去除，通过总结新型多孔吸附材料用于放射性核素吸附分离的最新研究进展；着重讨论了新型多孔吸附材料的设计制备、放射性元素去除性能以及放射性元素去除机理；最后基于上述分析，提出目前新型多孔吸附材料用于放射性核素吸附分离存在的问题，如难以处理粉末状的新型多孔吸附材料，以及在极端化学条件下容易出现结构不稳定的问题，并对未来的相关研究方向进行了展望，例如将研究从纯粹的基础研究扩展到更实用的方面和大力开发有效的合成方法，以获得高产率且无副产物的产品。

关键词: 多孔材料, 放射性核素, 量子筛分, 动态扩散, 高效分离

Abstract:

For the removal of radioactive elements by traditional adsorbents, there are shortcomings such as long adsorption time and unsatisfactory adsorption effect. The new porous adsorbent materials such as covalent organic frameworks (COF), metal-organic frameworks (MOF) and conjugated microporous polymers (CMP) have higher separation efficiencies for radionuclide separation due to the excellent physicochemical properties, high specific surface area, high porosity, fast charge-carrier mobility and tunable functionality. This paper focused on the removal of radioactive elements by various new porous adsorption materials, such as covalent organic frameworks (COF), metal organic frameworks (MOF) and highly crosslinked polymers (HCP) by summarizing the latest research progress on the use of new porous adsorption materials for the adsorption and separation of radioactive nuclides. The design and preparation of new porous adsorption materials, the removal performance of radioactive elements and the removal mechanism of radioactive elements were emphasized. Finally, based on the above analysis, the current problems of new porous adsorbent materials for radionuclide adsorption and separation, such as the difficulty of dealing with new porous adsorbent materials in powder form and the problem of structural instability under extreme chemical conditions, were proposed. The future directions of the research were also envisioned, such as expanding the research from purely basic research to more practical aspects and vigorously development of effective synthesis methods to obtain products with high yields and no by-products.

Key words: spongy substance, radionuclides, quantum sieving, dynamic diffusion, efficient separation

中图分类号:

TB334

焦芮, 周涛, 孙寒雪, 李吉焱, 朱照琪, 李安. 多孔材料用于废水中放射性核素吸附的研究进展[J]. 化工进展, 2025, 44(1): 354-366.

JIAO Rui, ZHOU Tao, SUN Hanxue, LI Jiyan, ZHU Zhaoqi, LI An. Progress in the study of porous materials for radionuclide adsorption in wastewater[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 354-366.

图/表 12

表1 不同放射性废水处理技术的特点与局限

处理技术	特点	局限性	参考文献
化学沉淀	工艺简单、成本低、适用范围广	固液分离困难、污泥量大、会造成二次污染	[2-3]
离子交换	具有良好的化学稳定性、热稳定性和辐射稳定性	无法用于处理高浓度放射性废水；难以循环利用	[4-5]
膜分离技术	净化系数高、浓缩量大、能耗低、系统简单、操作灵活	材料的成膜性较难；膜寿命较短	[6-9]
蒸发浓缩	净化系数和体积减量效果高、灵活性大、应用范围广、能够与各种技术相结合	热利用率低，价格昂贵；不适用于处理含有挥发性核素的废液；处理酸性高放废液时，随着酸浓度的增加，沸点升高，效率降低，设备腐蚀性增加	[10-11]
物理吸附	吸附材料种类多，可根据不同放射性核素的性质选择与之相对应的吸附剂	材料再生性能差、成本高	[12-13]

图1 NT-COF的结构模型[28]

图2 DHNDA和TAPP的缩合以及烯醇和酮形式之间的同分异构合成COF[35]

图3 δ-MnO2@TpPa-1复合材料和KTG水凝胶的吸附机理及其吸附铀元素性能[39-40]

图4 COF-TpDb-AO、COF/GO和TFPT-BTAN-AO的合成示意图及其吸附铀元素性能[41-43]

图5 C6-TRZ-TPA COF和COF-LZU1的合成及其吸附碘元素性能[44-45]

图6 SCU-COF-1和DhaTGCl的合成及其吸附ReO4-性能；TT-Por COF-Ni和COF 2-Ru-AO的合成以及利用光催化法处理铀元素性能[46-49]

图7 不同种类MOF材料[50]

图8 MILP、MIL-101-DETA和UiO-66-NH2@CS-PDA的合成以及吸附铀元素性能[59-61]

图9 MIL-125-NH2和PCN-333(Al)的吸附机理与结构以及吸附碘元素性能[62-63]

图10 CaONPs@MOF-5去除Sr2+性能、NZVI@PCN-224光催化机理与合成以及处理铀元素性能以及Zr/Ti-MOFs的光催化过程[66-68]

图11 CPP和PAF-1-CH2AO的合成以及吸附铀元素性能[71-72]

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