Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation

doi:10.1021/acs.inorgchem.9b03604

CORC > 宁波材料技术与工程研究所 > 中国科学院宁波材料技术与工程研究所 > 2020专题

	Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation
	Chen, Yan-Mei ; Wang, Cong-Zhi ; Wu, Qun-Yan ; Lan, Jian-Hui ; Chai, Zhi-Fang ; Nie, Chang-Ming ; Shi, Wei-Qun
刊名	INORGANIC CHEMISTRY
	2020
卷号	59 期号:5 页码:3221-3231
关键词	SEGMENTED CONTRACTION SCHEME EFFICIENT SEPARATION VALENCE INDEXES MINOR ACTINIDES COMPLEXATION EXTRACTION LANTHANIDES SELECTIVITY COVALENCY DESIGN
DOI	10.1021/acs.inorgchem.9b03604
英文摘要	Nitrogen-donor ligands have been considered to be promising agents for separating trivalent actinides (An(III)) from lanthanides (Ln(III)). Thereinto, how to decorate these ligands for better extraction performance is urgent to design "perfect" separating extractants. In this work, we systematically explored a series of heterocyclic N-donor ligands (L-1 = dipyridazino[4,3-c:3',4'-h]acridine, L-2 = dipyridazino[3,4-a:4',3'-j]phenazine, L-3 = 2,6-di(cinnolin-3-yl)pyridine)), as well as their substituted derivatives, and compared their extraction and complexation ability toward An(III) and Ln(III) ions by using quasi-relativistic density functional theory (DFT). We found that the pyridazine N atoms probably play a notable role in electron donation to metal cations by molecular orbital (MO) and bond order analyses. Besides, the calculated results clearly verified that these N-donor ligands possess higher coordination affinity toward Am(III) over Eu(III). The rigid ligands (L-1 and L-2) exhibit higher selective abilities for the Am(III)/Eu(III) separation compared with that of the flexible ligand (L-3). For each ligand, the 1:2 (metal/ligand) extraction reaction is predicted to be most probable in the separation process. The introduction of an alkyl group on the lateral chain or an electron-donating group on the main chain gives rise to a better extraction performance of the ligands, and the CyMe4 or MeO substituted ligands show higher extraction and separation ability. Simultaneous introduction of CyMe4 and MeO groups can enhance the extraction ability of the ligand to metal ions, but the separating ability depends on the differences of the extraction capacity of An(III) and Ln(III). This work can help to gain a more in-depth understanding the selectivity differences of similar N-donor ligands and provide more theoretical insights into the design of novel extractants for An(III)/Ln(III) separation.
学科主题	Chemistry
内容类型	期刊论文
源URL	[http://ir.nimte.ac.cn/handle/174433/19896]
专题	2020专题
作者单位	1.Shi, WQ (corresponding author), Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China. 2.Nie, CM (corresponding author), Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
推荐引用方式 GB/T 7714	Chen, Yan-Mei,Wang, Cong-Zhi,Wu, Qun-Yan,et al. Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation[J]. INORGANIC CHEMISTRY,2020,59(5):3221-3231.
APA	Chen, Yan-Mei.,Wang, Cong-Zhi.,Wu, Qun-Yan.,Lan, Jian-Hui.,Chai, Zhi-Fang.,...&Shi, Wei-Qun.(2020).Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation.INORGANIC CHEMISTRY,59(5),3221-3231.
MLA	Chen, Yan-Mei,et al."Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation".INORGANIC CHEMISTRY 59.5(2020):3221-3231.