Complexation and Separation of Trivalent Actinides and Lanthanides by a Novel DGA Derived from Macrocyclic Crown Ether: Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies.
Complexation and Separation of Trivalent Actinides and Lanthanides by a Novel DGA Derived from Macrocyclic Crown Ether: Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies.
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由大环冠醚衍生的新型 DGA 络合和分离三价锕系元素和镧系元素：合成、萃取以及光谱和密度泛函理论研究
DOI：
10.1021/acsomega.0c05317
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发表时间：
2021-01-26
期刊：
影响因子：
4.1
通讯作者：
Xia C
中科院分区：
文献类型：
--
作者：
Fan Y;Li Y;Shu X;Wu R;Chen S;Jin Y;Xu C;Chen J;Huang C;Xia C
合成了一种大环氮杂冠醚配体（Cr 6DGA），并研究了其在硝酸介质中对三价铕和镅的萃取行为。考察了接触时间、温度、萃取剂浓度、酸度等因素对Cr 6DGA萃取的影响。结果表明，在3 mol/L HNO 3溶液中，SFEu/Am值约为2。通过密度泛函理论计算的络合能表明，Eu（III）配合物比相应的Am（III）配合物在气相，水相和有机相中更稳定。此外，配位研究表明，通过质谱（MS）分析，提取物质的金属/配体比为1：2。时间分辨激光诱导荧光光谱（TRLFS）进一步证明了萃取物中含有一个水分子，因此萃取物的组成可能是[EuL 2（NO3）2（H2O）]2+或[EuL 2（NO3）2（H2O）]+。最后，DFT计算表明[EuL 2（NO3）2（H2O）]+是一个更稳定的物种，Eu（III）与DGA单元的结合能低于与冠醚单元的结合能.
A DGA-arm-grafted macrocyclic aza-crown ether ligand (Cr6DGA) was synthesized, and its solvent extraction behavior toward trivalent americium and europium in nitric acid medium was studied. The effects of various parameters such as the contact time, temperature, concentration of the extractant, and acidity on the extraction by Cr6DGA were investigated. It was found that in 3 mol/L HNO3, the SFEu/Am value was about 2. The complexation energies calculated by DFT showed that the Eu(III) complexes were more stable than the corresponding Am(III) complexes in gas, aqueous, and organic phases. Furthermore, the coordination study showed that the metal/ligand ratio of the extracted species was 1:2 by mass spectrometry (MS) analysis. The time-resolved laser-induced fluorescence spectra (TRLFS) further proved that the extracted species contained one water molecule, and so the composition of the extracted complexes may be [EuL2NO3(H2O)]2+ or [EuL2(NO3)2(H2O)]+. Finally, DFT calculations revealed that [EuL2(NO3)2(H2O)]+ is a more stable species and the binding energy of Eu(III) with the DGA unit is lower than that with the crown unit.
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影响因子：
4.6
作者：
Hudson, Michael J.;Harwood, Laurence M.;Lewis, Frank W.
通讯作者：
Lewis, Frank W.
影响因子：
15
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Brigham, Derek M.;Ivanov, Alexander S.;Ellis, Ross J.
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Ellis, Ross J.
影响因子：
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作者：
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通讯作者：
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影响因子：
4.4
作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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