Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides

	Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides
	Wang CZ(王聪芝); Lan JH(蓝建慧); Wu QY(吴群燕); Wang, CZ; Lan, JH; Wu, QY; Zhao, YL; Wang, XK; Chai, ZF; Shi, WQ;
刊名	DALTON TRANSACTIONS
	2014
卷号	43 期号:23 页码:8713-8720
英文摘要	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(NO3)(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.
学科主题	Chemistry
收录类别	SCI
WOS记录号	WOS:000336800700017
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/224988]
专题	高能物理研究所_院士高能物理研究所_多学科研究中心
推荐引用方式 GB/T 7714	Wang CZ,Lan JH,Wu QY,et al. Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides[J]. DALTON TRANSACTIONS,2014,43(23):8713-8720.
APA	王聪芝.,蓝建慧.,吴群燕.,Wang, CZ.,Lan, JH.,...&石伟群.(2014).Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides.DALTON TRANSACTIONS,43(23),8713-8720.
MLA	王聪芝,et al."Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides".DALTON TRANSACTIONS 43.23(2014):8713-8720.