基于铀酰多元配位的磁性异质杯芳烃功能材料及其促铀分离富集机理

As the nuclear power projects having been restarted and the central government acelerating the "going out" strategy of the nuclear power, the supply of natural uranium resources is still under pressure. Therefore, studies on the new method of extracting the uranium from the low grade uranium mines and separating-enriching the uranium from the waste water containing low concentration of uranium, have important strategic significance. Based on the space coordination configuration of uranyl ion, some novel magnetic heterogeneous calixarene functional materials would be prepared by graft loading with the modified magnetic nanosized Fe3O4 and the function hybrid calix[4]arene derivatives through N-acylation-reaction, through the functional modification under the calix[4]arene using containing S, P, N heteroatomic groups, and the derivation active functional groups uper the calix[4]arene which having mul-coordination function for UO22+. And the functional materials must be three-dimensional conformation stability, the space coordination configuration matching and mul-coording to UO22+. The theory evidence of selective separating-enriching the uranium would be builded from the waste water containing low concentration of uranium, which would be completed by characterizing the morphology, analysis the quantitative relationship of interface structure and performance of the functional materials by SEM, TEM, FTIR and XRD, analyzing the contribute of each functional group on separating-enriching Uranium. And the separation and enrichment method of uranium would be established which having a high selectivity, high enrichment ratio and the stable performance, the selective adsorption of uranium would be studied, the mechanism of promoting the separation.and enrichment of uranium would also studied. At the same time, it would be supported to the safe produce in the Uranium mines and remediation of the entironment around tailings areas of uranium mines. This work is feasible with brilliant prospected and scientific significance.

随着核电项目的陆续重启和中央加快推进核电“走出去”战略，天然铀资源供应仍面临巨大压力。因此，研究低品位铀矿中铀的提取和含铀废水中低浓度铀的分离富集新方法，对铀资源化和有害辐射防护具有重要的战略意义。本项目从铀酰离子的空间配位构型出发，拟对杯[4]芳烃下沿进行功能杂化修饰，上沿羧基化修饰，衍生对UO22+具有多元配位功能的活性基团，并将其“接枝负载”改性后的磁性纳米Fe3O4粒子，制备立体构象稳定、空间配位构型匹配并对UO22+多元配位的磁性异质杯芳烃功能材料。通过功能材料的形貌变化、界面结构与性能的定量关系分析，研究各个功能配位基团在促铀分离富集中的作用与贡献，并建立具有高选择性、高富集率和性能稳定的分离富集铀的方法，考察对铀的选择性吸附性能，揭示促铀分离富集机理，为功能材料应用于铀选择性分离富集提供理论依据。本项目对指导铀厂矿安全生产和尾矿库有害辐射防护等方面具有重要的应用价值。

随着国民经济的快速发展，能源短缺问题变得越来越严重，核能作为一种高效清洁的能源受到更加广泛的重视。铀是核能的主要燃料，它具有化学毒性和放射性。在铀矿冶过程中会产生大量的含铀废水，若不妥善处理，将会对生态环境和人类健康产生巨大危害。因此，研究低浓度含铀废水中铀的分离富集新方法，对铀资源化和有害辐射防护具有重要的战略意义。. 在本项目中，我们根据铀酰离子的结构特点，选择杯[4]芳烃作为母体骨架，先用S、N和P等杂原子基团对其下沿进行修饰，然后对其上沿进行羧基化衍生，最后“接枝负载”到表面氨基化的磁性纳米Fe3O4粒子上。对于杯[4]芳烃下沿修饰，我们成功制备了杯[4]芳烃偕胺肟衍生物、杯[4]芳烃对称硫醚衍生物、杯[4]芳烃磷酸酯衍生物等，并研究了它们对铀分离富集机理，发现它们均对铀具有良好的选择性分离能力和重复使用能力；对于杯[4]芳烃上沿羧基化衍生，我们成功制备了功能化偶氮杯[4]芳烃羧基衍生物和对羧基苯偶氮基杯[4]芳烃磷酸酯衍生物，并研究了它们对铀分离富集机理，发现上沿改性之后杯[4]芳烃的独特构型未遭破坏，对铀的分离效率也未见下降；对于杯[4]芳烃与磁性纳米Fe3O4粒子的“接枝负载”，我们制备了磁性功能改性杯[4]芳烃胺肟衍生物和磁性功能化杯[4]芳烃复合材料，并研究了它们对铀的分离富集机理，发现磁性功能化的杯[4]芳烃因具有顺磁性和大的比表面积而使其对铀分离富集效率更高。. 在项目研究期间，本项目组共发表论文13篇，申请和授权专利5项，培养硕士研究生6位，圆满完成了工作内容，达到了预期目标。本项目的开展为杯芳烃的修饰提供了参考方法，也为杯芳烃功能材料对含铀废水的处理提供了理论依据，对于环境修复和有害辐射防护等方面具有指导意义。