IHEP OpenIR  > 多学科研究中心
Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study
Kong XH(孔祥鹤); Wu QY(吴群燕); Wang CZ(王聪芝); Lan JH(蓝建慧); Chai ZF(柴之芳); Shi WQ(石伟群); Kong, XH; Wu, QY; Wang, CZ; Lan, JH; Chai, ZF; Nie, CM; Shi, WQ
2018
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume122Issue:18Pages:4499-4507
SubtypeArticle; Proceedings Paper
AbstractSeparation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is one of the most important steps in spent nuclear fuel reprocessing. However, it is very difficult and challenging to separate them due to their similar chemical properties. Recently the pyridylpyrazole ligand (PypzH) has been identified to show good separation ability toward Am(III) over Eu(III). In this work, to explore the Am(III)/Eu(III) separation mechanism of PypzH at the molecular level, the geometrical structures, bonding nature, and thermodynamic behaviors of the Am(III) and Eu(III) complexes with PypzH ligands modified by alkyl chains (Cn-PypzH, n = 2, 4, 8) have been systematically investigated using scalar relativistic density functional theory (DFT). According to the NBO (natural bonding orbital) and QTAIM (quantum theory of atoms in molecules) analyses, the M-N bonds exhibit a certain degree of covalent character, and more covalency appears in Am-N bonds compared to Eu-N bonds. Thermodynamic analyses suggest that the 1:1 extraction reaction, [M(NO3)(H2O)(6)](2+) + PypzH + 2NO(3)(-) -> M(PypzH)(NO3)(3)(H2O) + 5H(2)O, is the most suitable for Am(III)/Eu(III) separation. Furthermore, the extraction ability and the Am(III)/Eu(III) selectivity of the ligand PypzH is indeed enhanced by adding alkyl-substituted chains in agreement with experimental observations. Besides this, the nitrogen atom of pyrazole ring plays a more significant role in the extraction reactions related to Am(III)/Eu(III) separation compared to that of pyridine ring. This work could identify the mechanism of the Am(III)/Eu(III) selectivity of the ligand PypzH and provide valuable theoretical information for achieving an efficient Am(III)/Eu(III) separation process for spent nuclear fuel reprocessing.
Conference Title18th Meeting on Time-Resolved Vibrational Spectroscopy (TRVS)
Conference PlaceCambridge, ENGLAND
DOI10.1021/acs.jpca.8b00177
WOS KeywordDENSITY-FUNCTIONAL THEORY ; SEGMENTED CONTRACTION SCHEME ; PSEUDOPOTENTIAL BASIS-SETS ; ACTINIDE(III)/LANTHANIDE(III) SEPARATION ; SELECTIVE EXTRACTION ; ELECTRONIC-STRUCTURE ; TRIVALENT ACTINIDE ; COMPLEXES ; LANTHANIDE ; LIGANDS
Indexed BySCI ; ADS ; EI ; CPCI
Language英语
WOS Research AreaChemistry ; Physics
WOS SubjectChemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS IDWOS:000432204200014
EI Accession Number20181905151775
ADS Bibcode2018JPCA..122.4499K
ADS URLhttps://ui.adsabs.harvard.edu/abs/2018JPCA..122.4499K
ADS CITATIONShttps://ui.adsabs.harvard.edu/abs/2018JPCA..122.4499K/citations
Citation statistics
Cited Times:2 [ADS]
Document Type期刊论文
Identifierhttp://ir.ihep.ac.cn/handle/311005/285914
Collection多学科研究中心
Corresponding AuthorShi WQ(石伟群)
Affiliation中国科学院高能物理研究所
First Author AffilicationInstitute of High Energy
Corresponding Author AffilicationInstitute of High Energy
Recommended Citation
GB/T 7714
Kong XH,Wu QY,Wang CZ,et al. Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2018,122(18):4499-4507.
APA 孔祥鹤.,吴群燕.,王聪芝.,蓝建慧.,柴之芳.,...&Shi, WQ.(2018).Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study.JOURNAL OF PHYSICAL CHEMISTRY A,122(18),4499-4507.
MLA 孔祥鹤,et al."Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study".JOURNAL OF PHYSICAL CHEMISTRY A 122.18(2018):4499-4507.
Files in This Item:
File Name/Size DocType Version Access License
20180430.pdf(2913KB)期刊论文出版稿限制开放CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[孔祥鹤]'s Articles
[吴群燕]'s Articles
[王聪芝]'s Articles
Baidu academic
Similar articles in Baidu academic
[孔祥鹤]'s Articles
[吴群燕]'s Articles
[王聪芝]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[孔祥鹤]'s Articles
[吴群燕]'s Articles
[王聪芝]'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.