The redox mechanism of Np-VI with hydrazine: a DFT study

doi:10.1039/C6RA13339H

	The redox mechanism of Np-VI with hydrazine: a DFT study
	Wu QY(吴群燕); Lan JH(蓝建慧); Wang CZ(王聪芝); Cheng ZP(程仲平); Chai ZF(柴之芳); Shi WQ(石伟群); Cheng, ZP; Wu, QY; Liu, YH; Lan, JH
刊名	RSC ADVANCES
	2016
卷号	6 期号:110 页码:109045-109053
DOI	10.1039/C6RA13339H
通讯作者	石伟群
英文摘要	Valence state control and adjustment of neptunium in spent fuel reprocessing is very important for improving the separation efficiency of U/Np and Np/Pu. Hydrazine and its derivatives have been experimentally demonstrated to be effective in the reduction of Np-VI to Np-V. In this work, hydrazine was used as a representative reductant and the reduction mechanisms of Np-VI induced by hydrazine were investigated using density functional theory (DFT) calculations. Three reaction pathways were taken into account and characterized by gradually transferring a hydrogen atom from N2H4 to the "yl"-oxygen of [(NpO2)-O-VI(H2O)(5)](2+) followed by the valence state adjustment from Np-VI to Np-V. The calculated results of the potential energy profiles (PEPs) revealed that Pathway I should be the most likely to occur as the process of forming (N2H3)-N-center dot is considered to be the rate-determining step with the highest energy barrier of 32.02 kcal mol(-1), which is in favor of the experimental results. Pathway II hardly occurs and Pathway III probably occurs. The bonding evolution, along with the reaction pathways, was explored through natural bond orbitals (NBOs), quantum theory of atoms-in-molecules (QTAIM) and electron localization function (ELF) analyses. This work can shed light on the understanding of redox mechanisms of Np-VI with N2H4 and its derivatives and help further attempts to design more efficient reductants for the separation of U/Np and Np/Pu in spent nuclear fuel reprocessing in the near future.
语种	英语
WOS记录号	WOS:000389342800101
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/261074]
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
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	Wu QY,Lan JH,Wang CZ,et al. The redox mechanism of Np-VI with hydrazine: a DFT study[J]. RSC ADVANCES,2016,6(110):109045-109053.
APA	吴群燕.,蓝建慧.,王聪芝.,程仲平.,柴之芳.,...&Shi, WQ.(2016).The redox mechanism of Np-VI with hydrazine: a DFT study.RSC ADVANCES,6(110),109045-109053.
MLA	吴群燕,et al."The redox mechanism of Np-VI with hydrazine: a DFT study".RSC ADVANCES 6.110(2016):109045-109053.