Selective Extraction of Uranium(VI) from Thorium(IV) Using New Unsymmetrical Acidic Phenanthroline Carboxamide Ligands,Industrial & Engineering Chemistry Research

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Selective Extraction of Uranium(VI) from Thorium(IV) Using New Unsymmetrical Acidic Phenanthroline Carboxamide Ligands
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2023-09-14 , DOI: 10.1021/acs.iecr.3c02101
Shihui Wang ₁ , Xiaofan Yang ₁ , Lei Xu _{2,

3} , Yujie Miao ₁ , Xiao Yang ₁ , Chengliang Xiao _{1,

3}

Affiliation

In the thorium–uranium fuel cycle, ²³²Th will produce fissional ²³³U and radioactive ²³²U simultaneously after irradiation. The selective separation of uranium from thorium-based spent fuel can enhance the utilization efficiency of nuclear fuel and promote the safety of nuclear energy utilization. In this work, a new type of unsymmetrical acidic phenanthroline carboxamide ligand represented as 9-(N,N-dialkylcarbamoyl)-1,10-phenanthroline-2-carboxylic acid (DEAPA and DOAPA) was synthesized for selective separation of U(VI) over Th(IV). The separation of small amounts of U(VI) from large amounts of Th(IV) could be achieved by using DOAPA to extract at high acidity (4 M HNO₃) and then using 1 M HNO₃ as the stripping agent. The complexation mechanism of these two ligands with U(VI) and Th(IV) was investigated through slope analysis, NMR spectrometric titration, UV–vis spectrophotometric titration, and single-crystal X-ray diffraction methods. Results from slope analysis and NMR spectrometric titration showed that DOAPA formed a 1:1 complex with U(VI) and formed 1:1 and 1:2 complexes with Th(IV). The larger stability constants (log β) of 1:1 complexes of DEAPA/DOAPA with U(VI) than those with Th(IV) implied the stronger affinity of the ligands with U(VI), which was in good coincidence with the solvent extraction results. The crystal structures of the 1:1 complex of U(VI) and the two species of 1:1 and 1:2 complexes of Th(IV) with DEAPA were successfully analyzed by X-ray diffraction. This work provided a new type of unsymmetrical acidic phenanthroline carboxamide extractant for the efficient separation of U(VI) from Th(IV). The systematic study of the extraction and complexation behavior would be helpful to explore the effect of functional groups as well as design extractants with excellent performance.

中文翻译：

使用新型不对称酸性菲咯啉甲酰胺配体从钍 (IV) 中选择性萃取铀 (VI)

在钍铀燃料循环中，²³² Th辐照后会同时产生裂变²³³ U 和放射性^{232 U。}从钍基乏燃料中选择性分离铀可以提高核燃料的利用效率，促进核能利用的安全。本工作合成了一种新型不对称酸性菲咯啉甲酰胺配体，以9-( N , N-二烷基氨基甲酰基)-1,10-菲咯啉-2-羧酸（DEAPA和DOAPA）为代表，用于选择性分离U(VI)超过 Th(IV)。通过使用 DOAPA 在高酸度（4 M HNO ₃），然后使用 1 M HNO ₃作为剥离剂。通过斜率分析、核磁共振光谱滴定、紫外-可见分光光度滴定和单晶X射线衍射方法研究了这两种配体与U(VI)和Th(IV)的络合机理。斜率分析和NMR谱滴定结果表明DOAPA与U(VI)形成1:1配合物，与Th(IV)形成1:1和1:2配合物。DEAPA/DOAPA与U(VI)的1:1配合物比与Th(IV)的配合物具有更大的稳定常数(log β)，这意味着配体与U(VI)的亲和力更强，这与溶剂吻合良好提取结果。通过X射线衍射成功分析了U(VI)的1:1配合物以及Th(IV)与DEAPA的1:1和1:2两种配合物的晶体结构。该工作提供了一种新型的不对称酸性菲咯啉甲酰胺萃取剂，用于高效分离 U(VI) 和 Th(IV)。对萃取和络合行为的系统研究将有助于探索官能团的作用以及设计性能优异的萃取剂。

更新日期：2023-09-14

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