Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands
文献类型：期刊论文
| 作者 | Liu, Yang; Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Chai, Zhi-Fang; Liu, Qi; Shi, Wei-Qun |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2021 |
| 卷号 | 60期号:14页码:10267-10279 |
| 关键词 | ACIDIC-SOLUTION ACTINIDES COMPLEXES DENSITY ENERGY LANTHANIDES COVALENCY AMERICIUM(III) CALIFORNIUM SELECTIVITY |
| 英文摘要 | In the process of spent fuel reprocessing, it is highly difficult to extract transplutonium elements from adjacent actinides. A deep understanding of the electronic structure of transplutonium complexes is essential for development of steady ligands for in-group separation of transplutonium actinides. In this work, we have systematically explored the potential in-group separation ability of transplutonium elements of typical quadridentate N-donor ligands (phenanthroline-derived bis-triazine, BTPhen derivatives) through quasi-relativistic density functional theory (DFT). Our calculations demonstrate that ligands with electron-donating groups have stronger coordination abilities, and the substitutions of Br and phenol at the 4-position of the 1,10-phenanthroline have a higher effect on the ligand than those at the 5-position. Bonding analysis indicates that the covalent interaction of An(3+) complexes becomes stronger from Am to Cf apart from Cm, which is because the energy of the 5f orbital gradually decreases and becomes energy-degenerate with the 2p orbitals of ligands. The most negative values of binding energies indicate the higher stability of Cf3+ complexes, in line with the larger covalency in the Cf-L bonds compared with An-L (An = Am, Cm, Bk). In addition, electron-donating group phenol can enhance the covalent interaction between ligands and heavy actinides. Consequently, the extraction ability of ligands with electron-donating substituents for heavy actinides is generally stronger than other ligands. Nevertheless, these ligands exhibit diverse separation abilities to in-group actinide recovery. Therefore, the enhancement of covalency does not necessarily lead to the improvement of separation ability, which may be caused by different extraction abilities. Compared with the tetradentate N, O-donor ligands (2,9-diamide-1,10-phenanthrolinel, DAPhen derivatives), species with BTPhen ligands display stronger covalent interaction and higher extraction capacity. In terms of in-group separation ability, the BTPhen ligands seem to have advantages in separation of californium from curium, while the DAPhen ligands possess stronger abilities to separate americium from curium. These results may afford some afflatus for the development of effective agents for in-group separation of transplutonium elements. |
| 源URL | [http://ir.nimte.ac.cn/handle/174433/21731]  |
| 专题 | 中国科学院宁波材料技术与工程研究所 2021专题_期刊论文 |
| 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.Liu, Q (corresponding author), Harbin Engn Univ, Key Lab Superlight Mat & Surface Technol, Minist Educ, Coll Mat Sci & Chem Engn, Harbin 150001, Peoples R China. |
| 推荐引用方式 GB/T 7714 | Liu, Yang,Wang, Cong-Zhi,Wu, Qun-Yan,et al. Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands[J]. INORGANIC CHEMISTRY,2021,60(14):10267-10279. |
| APA | Liu, Yang.,Wang, Cong-Zhi.,Wu, Qun-Yan.,Lan, Jian-Hui.,Chai, Zhi-Fang.,...&Shi, Wei-Qun.(2021).Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands.INORGANIC CHEMISTRY,60(14),10267-10279. |
| MLA | Liu, Yang,et al."Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands".INORGANIC CHEMISTRY 60.14(2021):10267-10279. |
入库方式： OAI收割
来源：宁波材料技术与工程研究所
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