The redox mechanism of Np-VI with hydrazine: a DFT study
文献类型：期刊论文
| 作者 | 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
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| 刊名 | RSC ADVANCES
 |
| 出版日期 | 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 |
| 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. |
入库方式： OAI收割
来源：高能物理研究所
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