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Perrhenate and pertechnetate complexation by an azacryptand in nitric acid medium.
Dalton Transactions ( IF 4 ) Pub Date : 2020-01-09 , DOI: 10.1039/c9dt04314d
Alexiane Thevenet 1 , Cécile Marie , Christelle Tamain , Valeria Amendola , Ana Miljkovic , Dominique Guillaumont , Nathalie Boubals , Philippe Guilbaud
Affiliation  

Technetium is present as the pertechnetate anion in spent nuclear fuel solutions, and its extraction by several extractant systems is a major problem for the liquid-liquid extraction processes used to separate uranium and plutonium. To prevent technetium extraction into the organic phase, a complexing agent may be added to the aqueous nitric acid phase to selectively bind the pertechnetate anion. In the present study, liquid-liquid extraction experiments reveal that technetium distribution ratios are considerably lowered with addition of an azacryptand, which is a good receptor for pertechnetate anion recognition. This ligand is able to overcome the Hofmeister bias and selectively bind techetium in nitric acid solution. Coordination studies using infrared and Raman spectoscopies and DFT calculations show the formation of an inclusion complex with hydrogen bonds stabilizing the oxo-anion within the cavity. For the first time, the cage molecules are studied for an extraction process.

中文翻译:

高氮酸盐和高tech酸盐在硝酸介质中通过氮杂配体络合。

spent作为乏核燃料溶液中的高tech酸根阴离子存在,对于用于分离铀和p的液-液萃取过程,by的萃取体系是一个主要问题。为了防止tech提取到有机相中,可以将络合剂添加到硝酸水相中以选择性地结合高tech酸根阴离子。在目前的研究中,液-液萃取实验表明,添加了氮杂土的tech分布比例大大降低,而氮杂土是高tech酸阴离子识别的良好受体。该配体能够克服霍夫迈斯特偏见,并选择性地结合硝酸溶液中的tech。使用红外光谱和拉曼光谱以及DFT计算进行的配位研究表明,形成了带有氢键的包合物,稳定了空腔中的氧阴离子。第一次,研究了笼状分子的提取过程。
更新日期:2020-02-10
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