Theoretically unraveling the separation of Am(III)/Eu(III): insights from mixed N,O-donor ligands with variations of central heterocyclic moieties
文献类型：期刊论文
| 作者 | Shi WQ(石伟群) ; Ji, L; Song, YT; Wu, QY; Wu QY(吴群燕); Wang, CZ; Chai, ZF; Shi, WQ; Wang CZ(王聪芝); Chai ZF(柴之芳)
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| 刊名 | PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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| 出版日期 | 2017 |
| 卷号 | 19期号:39页码:26969-26979 |
| ISSN号 | 1463-9076 |
| DOI | 10.1039/c7cp04625a |
| 文献子类 | Article |
| 英文摘要 | With the fast development of nuclear energy, the issue related to spent nuclear fuel reprocessing has been regarded as an imperative task, especially for the separation of minor actinides. In fact, it still remains a worldwide challenge to separate trivalent An(III) from Ln(III) because of their similar chemical properties. Therefore, understanding the origin of extractant selectivity for the separation of An(III)/Ln(III) by using theoretical methods is quite necessary. In this work, three ligands with similar structures but different bridging frameworks, Et-Tol-DAPhen (L-a), Et-Tol-BPyDA (L-b) and Et-Tol-PyDA (L-c), have been investigated and compared using relativistic density functional theory. The electrostatic potential and molecular orbitals of the ligands indicate that ligand L-a is a better electron donor compared to ligands L-b and L-c. The results of QTAIM, NOCV and NBO suggest that the Am-N bonds in the studied complexes have more covalent character compared to the Eu-N bonds. Based on the thermodynamic analysis, [M(NO3)(H2O)(8)](2+) + L + 2NO(3)(-) = [ML(NO3)(3)] + 8H(2)O should be the most probable reaction in the solvent extraction system. Our results clearly verify that the relatively harder oxygen atoms offer these ligands higher coordination affinities toward both of the An(III) and Ln(III) ions compared to the relatively softer nitrogen atoms. However, the latter possess stronger affinities toward An(III) over Ln(III), which partly results in the selectivity of these ligands. This work can afford useful information on achieving efficient An(III)/Ln(III) separation through tuning the structural rigidity and hardness or softness of the functional moieties of the ligands. |
| 电子版国际标准刊号 | 1463-9084 |
| WOS关键词 | ACTINIDE-LANTHANIDE SEPARATION ; ELECTRON-DENSITY DISTRIBUTION ; SEGMENTED CONTRACTION SCHEME ; PSEUDOPOTENTIAL BASIS-SETS ; TRANSITION-STATE METHOD ; TRIVALENT ACTINIDE ; FUNCTIONAL THEORY ; IONIC-RADII ; COMPLEXES ; ENERGY |
| WOS研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000412763700051 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/284992]  |
| 专题 | 高能物理研究所_多学科研究中心 高能物理研究所_粒子天体物理中心 |
| 作者单位 | 中国科学院高能物理研究所 |
| 推荐引用方式 GB/T 7714 | Shi WQ,Ji, L,Song, YT,et al. Theoretically unraveling the separation of Am(III)/Eu(III): insights from mixed N,O-donor ligands with variations of central heterocyclic moieties[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2017,19(39):26969-26979. |
| APA | 石伟群.,Ji, L.,Song, YT.,Wu, QY.,吴群燕.,...&柴之芳.(2017).Theoretically unraveling the separation of Am(III)/Eu(III): insights from mixed N,O-donor ligands with variations of central heterocyclic moieties.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,19(39),26969-26979. |
| MLA | 石伟群,et al."Theoretically unraveling the separation of Am(III)/Eu(III): insights from mixed N,O-donor ligands with variations of central heterocyclic moieties".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 19.39(2017):26969-26979. |
入库方式： OAI收割
来源：高能物理研究所
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