A Fluorous Phosphate for the Effective Extraction of LnIII from Nitrate Media: Comparison with A Conventional Organic Phosphate
A Fluorous Phosphate for the Effective Extraction of LnIII from Nitrate Media: Comparison with A Conventional Organic Phosphate
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DOI：
10.1080/07366299.2021.1874115
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发表时间：
2021-02
影响因子：
2
通讯作者：
Y. Ueda;K. Kikuchi;K. Tokunaga;T. Sugita;N. Aoyagi;Kazuya Tanaka;H. Okamura
中科院分区：
文献类型：
--
作者：
Y. Ueda;K. Kikuchi;K. Tokunaga;T. Sugita;N. Aoyagi;Kazuya Tanaka;H. Okamura
摘要我们比较了新开发的荧光萃取剂Tris（4,4,5,5,6,6,7,7,7,7-7,7-7,7- nonofluoroheptyl）磷酸盐（TFP）磷酸盐（TFP）在荧光稀释液中，用于三价灯笼中带有常规有机提取物三丁基磷酸盐（TBP）的离子（LNIII）在N-辛烷值中。有机萃取剂TBP促进了碳氢化合物氟化的趋势，以减少提取性能，TFP在LNIII中的高分离因子表明TFP的分离性能优于TBP。通过比较提取的TFP和TBP复合物的配位环境，荧光相和有机相。终身测量和延长的X射线抽象细胞光谱法揭示了在提取阶段提取的络合物中EUIII的近乎协调环境，而在EUIII-TFP中几乎不存在EUIIII-TBP复合体另一方面，从宏观的角度来看，在EUIII提取过程中，水和硝酸盐阴离子转移到了提取阶段在有机阶段的水和NO3-阴离子与荧光相中的水数表明，水和No3-阴离子以某种方式损害了Euiii的萃取，因此可以用作荧光稀释剂中的TFP。 LNIII的替代提取和分离系统。
ABSTRACT We compare the extraction and separation performance of a newly developed fluorous extractant, tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in a fluorinated diluent perfluorohexane, for trivalent lanthanide ions (LnIII) with a conventional organic extractant, tri-n-butyl phosphate (TBP) in n-octane. Interestingly, the fluorinated extractant TFP exhibits a superior extraction performance for LnIII than the organic extractant TBP, despite the tendency of hydrocarbon fluorination to reduce the extraction performance. Furthermore, the high separation factors among LnIII by TFP suggest that the separation performance of TFP is superior to that of TBP. We proved the superior extraction and separation performance of TFP by comparing the coordination environment of the extracted TFP and TBP complexes, the fluorous phase, and the organic phase. From a microscopic perspective, luminescence lifetime measurements and extended X-ray absorption fine structure spectroscopy revealed the near coordination environment of EuIII in the extracted complex of the extracting phase. Hydrating water scarcely exists in the EuIII-TFP complex, while the EuIII-TBP complex has at least one hydrating water molecule. On the other hand, from a macroscopic perspective, water and nitrate anion transport into the extracting phase during EuIII extraction are revealing. The large amounts of water and NO3 − anions in the organic phase compared to those in the fluorous phase suggest that the extraction of water and NO3 − anions somehow impairs the extraction of EuIII into the organic phase. Hence, TFP in a fluorinated diluent can be used as an alternative extraction and separation system for LnIII.