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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides
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Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides

机译：三价镧系和act系元素与二甘醇酰胺的复合物的密度泛函理论研究

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At present, designing novel ligands for efficient actinide extraction in spent nuclear fuel reprocessing is extremely challenging due to the complicated chemical behaviors of actinides, the similar chemical properties of minor actinides (MA) and lanthanides, and the vulnerability of organic ligands in acidic radioactive solutions. In this work, a quantum chemical study on Am(III), Cm(III) and Eu(III) complexes with N,N,- N',N'-tetraoctyl diglycolamide (TODGA) and N,N'-dimethyl-N,N'-diheptyl-3-oxapentanediamide (DMDHOPDA) has been carried out to explore the extraction behaviors of trivalent actinides (An) and lanthanides (Ln) with diglycolamides from acidic media. It has been found that in the 1: 1 (ligand: metal) and 2: 1 stoichiometric complexes, the carbonyl oxygen atoms have stronger coordination ability than the ether oxygen atoms, and the interactions between metal cations and organic ligands are substantially ionic. The neutral ML(NO_3)_3 (M = Am, Cm, Eu) complexes seem to be the most favorable species in the extraction process, and the predicted relative selectivities are in agreement with experimental results, i.e., the diglycolamide ligands have slightly higher selectivity for Am(III) over Eu(III). Such a thermodynamical priority is probably caused by the higher stabilities of Eu(III) hydration species and Eu(III)-L complexes in aqueous solution compared to their analogues. In addition, our thermodynamic analysis from water to organic medium confirms that DMDHOPDA has higher extraction ability for the trivalent actinides and lanthanides than TODGA, which may be due to the steric hindrance of the bulky alkyl groups of TODGA ligands. This work might provide an insight into understanding the origin of the actinide selectivity and a theoretical basis for designing highly efficient extractants for actinide separation.
机译：目前，由于of系元素的复杂化学行为，次要act系元素（MA）和镧系元素的相似化学性质以及酸性放射性溶液中有机配体的脆弱性，为乏核燃料后处理中的高效efficient系元素提取设计新颖的配体极具挑战性。 。在这项工作中，对具有N，N，-N'，N'-四辛基二甘醇酰胺（TODGA）和N，N'-二甲基-N的Am（III），Cm（III）和Eu（III）配合物进行量子化学研究N'-二庚基-3-氧戊戊二酰胺（DMDHOPDA）已被用于研究酸性介质中二甘醇酰胺对三价act系元素（An）和镧系元素（Ln）的萃取行为。已经发现在1∶1（配体：金属）和2∶1化学计量的配合物中，羰基氧原子比醚氧原子具有更强的配位能力，并且金属阳离子和有机配体之间的相互作用基本上是离子性的。中性ML（NO_3）_3（M = Am，Cm，Eu）配合物似乎是萃取过程中最有利的物质，并且预测的相对选择性与实验结果相符，即二甘醇酰胺配体的选择性更高在Eu（III）上形成Am（III）。此类热力学优先级可能是由于Eu（III）水合物种和Eu（III）-L络合物在水溶液中的稳定性高于其类似物所致。此外，我们从水到有机介质的热力学分析证实，DMDHOPDA对三价act系元素和镧系元素的萃取能力比TODGA高，这可能是由于TODGA配体的大体积烷基的位阻所致。这项工作可能会提供深入了解understanding系元素选择性的起源，并为设计用于act系元素分离的高效萃取剂提供理论基础。

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