IHEP OpenIR  > 院士
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
2016
Source PublicationRSC ADVANCES
ISSN2046-2069
Volume6Issue:110Pages:109045-109053
Corresponding Author石伟群
SubtypeArticle
AbstractValence 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.
DOI10.1039/C6RA13339H
WOS KeywordNITRIC-ACID SOLUTION ; DENSITY-FUNCTIONAL THEORY ; TOPOLOGICAL ANALYSIS ; ELECTRON-DENSITY ; PUREX PROCESS ; THEORETICAL PERSPECTIVE ; SCREENING MODEL ; CHEMICAL-BONDS ; M(CO)(6) M=CR ; REAL SOLVENTS
Indexed BySCI ; ADS ; ADS
Language英语
WOS IDWOS:000389342800101
ADS Bibcode2016RSCAd...6j9045C
ADS URLhttps://ui.adsabs.harvard.edu/abs/2016RSCAd...6j9045C
ADS CITATIONShttps://ui.adsabs.harvard.edu/abs/2016RSCAd...6j9045C/citations
Citation statistics
Cited Times:3 [ADS]
Document Type期刊论文
Identifierhttp://ir.ihep.ac.cn/handle/311005/261074
Collection院士
多学科研究中心
Affiliation中国科学院高能物理研究所
Recommended Citation
GB/T 7714
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.
Files in This Item:
File Name/Size DocType Version Access License
20160918.pdf(1473KB)期刊论文作者接受稿限制开放CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[程仲平]'s Articles
[吴群燕]'s Articles
[蓝建慧]'s Articles
Baidu academic
Similar articles in Baidu academic
[程仲平]'s Articles
[吴群燕]'s Articles
[蓝建慧]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[程仲平]'s Articles
[吴群燕]'s Articles
[蓝建慧]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.