Stronger Hydration of Eu(III) Impedes Its Competition against Am(III) in Binding with N-donor Extractants.,Inorganic Chemistry

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Stronger Hydration of Eu(III) Impedes Its Competition against Am(III) in Binding with N-donor Extractants.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-04-13 , DOI: 10.1021/acs.inorgchem.0c00374
Miaoren Xia _{1,

2} , Xia Yang _{1,

3} , Zhifang Chai _{1,

2,

4} , Dongqi Wang _{1,

2}

Affiliation

The significance of understanding the interaction between actinide(III)/lanthanide(III) (An(III)/Ln(III)) and N-donor extractants lies in the importance of efficient An3+/Ln3+ separation in advanced nuclear fuel cycles and the high expectation of the application of N-donor extractants. This work reports a density functional theory study aiming at a plausible explanation of the origin of the selectivity of the ligands in An3+/Ln3+ separation and an evaluation of the influence of the bridging groups of typical N-donor extractants. Five bis(triazine) N-donor ligands were considered, differing in their denticity dictated by their bridging groups and in the flexibility of these bridging groups. The results showed much stronger hydration of Eu(III) in comparison to Am(III) in the ligand exchange of aqua ligands by N-donor ligands, while there was a moderate difference in their interaction strengths with the N-donor ligands. This implicated that the distinct difficulty in desolvating Eu(III) and Am(III) may govern their selectivity in liquid-liquid extraction. The analysis of the role of the bridging groups of the ligands confirmed the importance of a ligand to be equipped with preorganized binding sites to minimize the perturbation of entropy. We tentatively propose that this conclusion may hold in the explanation of the low selectivity of oxygenated extractants and the high selectivity of extractants with soft donors in An3+/Ln3+ separation.

中文翻译：

Eu（III）的强水化作用会阻止其与Am（III）与N-供体萃取剂的结合。

了解act系元素（III）/镧系元素（III）（An（III）/ Ln（III））与N供体萃取剂之间的相互作用的重要性在于，在先进核燃料循环中高效An3 + / Ln3 +分离和期望使用N供体萃取剂。这项工作报告了密度泛函理论研究，旨在对An3 + / Ln3 +分离中配体选择性的起源进行合理解释，并评估典型N供体萃取剂桥联基团的影响。考虑了五个双（三嗪）N-供体配体，它们的桥连基团所决定的密度和这些桥连基团的灵活性不同。结果表明，在通过N-供体配体进行水配体的配体交换中，与Am（III）相比，Eu（III）的水合作用强得多。而它们与N-供体配体的相互作用强度存在中等差异。这暗示了使Eu（III）和Am（III）脱溶剂的独特困难可能决定了它们在液-液萃取中的选择性。对配体桥联基团的作用的分析证实了配体要配备有预先组织好的结合位点以使熵的扰动最小化的重要性。我们初步提出，该结论可以解释为在An3 + / Ln3 +分离中，含氧萃取剂的低选择性和具有软供体的萃取剂的高选择性。对配体桥联基团的作用的分析证实了配体要配备有预先组织好的结合位点以使熵的扰动最小化的重要性。我们初步提出，该结论可以解释为在An3 + / Ln3 +分离中，含氧萃取剂的低选择性和具有软供体的萃取剂的高选择性。对配体桥联基团的作用的分析证实了配体要配备有预先组织好的结合位点以使熵的扰动最小化的重要性。我们初步提出，该结论可以解释为在An3 + / Ln3 +分离中，含氧萃取剂的低选择性和具有软供体的萃取剂的高选择性。

更新日期：2020-04-13

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