Theoretical studies on the AnO(2)(n+) (An = U, Np; n=1, 2) complexes with di-(2-ethylhexyl) phosphoric acid

	Theoretical studies on the AnO(2)(n+) (An = U, Np; n=1, 2) complexes with di-(2-ethylhexyl) phosphoric acid
	Luo J(罗娟); Wang CZ(王聪芝); Lan JH(蓝建慧); Wu QY(吴群燕); Zhao YL(赵宇亮); Chai ZF(柴之芳); Shi WQ(石伟群); Luo, J; Wang, CZ; Lan, JH
刊名	DALTON TRANSACTIONS
	2015
卷号	44 期号:7 页码:3227-3236
通讯作者	石伟群
英文摘要	Actinide separation in spent nuclear fuel reprocessing is essential for the closed nuclear fuel cycle. Organophosphorus reagents have been found to exhibit strong affinities for actinides in experiments. In this work, the extraction complexes of AnO(2)(n+) (An = U, Np; n = 1, 2) with the traditional organophosphorus ligand HDEHP (di-(2-ethylhexyl)phosphoric acid) have been investigated using density functional theory together with scalar-relativistic effective core potentials (ECPs) for actinide elements. According to our calculations, the HDEHP dimer prefers to act as a bidentate ligand in most of the studied complexes. HDEHP ligands show a higher extraction ability for An(VI) over An(V), and the formation of Np(VI) complexes is slightly more favorable than those of U(VI) analogues, which is mainly attributed to the stronger donoracceptor interaction in Np(VI) complexes. The intramolecular hydrogen bonds play a significant role in the stability of the 1 : 1 type complexes AnO(2)(HL)(2)(NO3)(2) (L = DEHP-). Moreover, AnO(2)(HL)(2)(NO3)(2) are the most stable species in nitrate-rich acid solutions, while at low nitric acid concentrations, the complexing reaction of AnO(2)(H2O)(5)(2+) + 2(HL)(2) -> AnO(2)(HL2)(2) + 2H(+) + 5H(2)O is probably the dominant reaction in the extraction process. Our results can help to understand the speciation of actinyl complexes in real solvent extraction of actinides with HDEHP at the molecular level.
学科主题	Chemistry
类目[WOS]	Chemistry, Inorganic & Nuclear
收录类别	SCI ; EI ; CA ; MEDLINE
WOS记录号	WOS:000349403100035
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/228172]
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	Luo J,Wang CZ,Lan JH,et al. Theoretical studies on the AnO(2)(n+) (An = U, Np; n=1, 2) complexes with di-(2-ethylhexyl) phosphoric acid[J]. DALTON TRANSACTIONS,2015,44(7):3227-3236.
APA	罗娟.,王聪芝.,蓝建慧.,吴群燕.,赵宇亮.,...&Shi, WQ.(2015).Theoretical studies on the AnO(2)(n+) (An = U, Np; n=1, 2) complexes with di-(2-ethylhexyl) phosphoric acid.DALTON TRANSACTIONS,44(7),3227-3236.
MLA	罗娟,et al."Theoretical studies on the AnO(2)(n+) (An = U, Np; n=1, 2) complexes with di-(2-ethylhexyl) phosphoric acid".DALTON TRANSACTIONS 44.7(2015):3227-3236.