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The redox mechanism of Np-VI with hydrazine: a DFT study
Cheng ZP(程仲平); Wu QY(吴群燕); Lan JH(蓝建慧); Wang CZ(王聪芝); Chai ZF(柴之芳); Shi WQ(石伟群); Cheng, ZP; Wu, QY; Liu, YH; Lan, JH; Wang, CZ; Chai, ZF; Shi, WQ
刊名RSC ADVANCES
2016
卷号6期号:110页码:109045-109053
DOI10.1039/C6RA13339H
通讯作者石伟群
文章类型Article
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.
关键词[WOS]NITRIC-ACID SOLUTION ; DENSITY-FUNCTIONAL THEORY ; TOPOLOGICAL ANALYSIS ; ELECTRON-DENSITY ; PUREX PROCESS ; THEORETICAL PERSPECTIVE ; SCREENING MODEL ; CHEMICAL-BONDS ; M(CO)(6) M=CR ; REAL SOLVENTS
语种英语
WOS记录号WOS:000389342800101
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文献类型期刊论文
条目标识符http://ir.ihep.ac.cn/handle/311005/261074
专题院士_期刊论文
中国科学院高能物理研究所_多学科研究中心
作者单位中国科学院高能物理研究所
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Cheng ZP,Wu QY,Lan JH,et al. The redox mechanism of Np-VI with hydrazine: a DFT study[J]. RSC ADVANCES,2016,6(110):109045-109053.
APA 程仲平.,吴群燕.,蓝建慧.,王聪芝.,柴之芳.,...&Shi, WQ.(2016).The redox mechanism of Np-VI with hydrazine: a DFT study.RSC ADVANCES,6(110),109045-109053.
MLA 程仲平,et al."The redox mechanism of Np-VI with hydrazine: a DFT study".RSC ADVANCES 6.110(2016):109045-109053.
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