Theoretically unraveling the separation of am(iii)/eu(iii): insights from mixed n,o-donor ligands with variations of central heterocyclic moieties
文献类型：期刊论文
| 作者 | Wu, Qun-Yan1,2; Song, Yu-Ting3; Ji, Lin3; Wang, Cong-Zhi1,2; Chai, Zhi-Fang1,2,4,5; Shi, Wei-Qun1,2 |
| 刊名 | Physical chemistry chemical physics
 |
| 出版日期 | 2017-10-21 |
| 卷号 | 19期号:39页码:26969-26979 |
| ISSN号 | 1463-9076 |
| DOI | 10.1039/c7cp04625a |
| 通讯作者 | Shi, wei-qun(shiwq@ihep.ac.cnni) |
| 英文摘要 | With the fast development of nuclear energy, the issue related to spent nuclear fuel reprocessing has been regarded as an imperative task, especially for the separation of minor actinides. in fact, it still remains a worldwide challenge to separate trivalent an(iii) from ln(iii) because of their similar chemical properties. therefore, understanding the origin of extractant selectivity for the separation of an(iii)/ln(iii) by using theoretical methods is quite necessary. in this work, three ligands with similar structures but different bridging frameworks, et-tol-daphen (l-a), et-tol-bpyda (l-b) and et-tol-pyda (l-c), have been investigated and compared using relativistic density functional theory. the electrostatic potential and molecular orbitals of the ligands indicate that ligand l-a is a better electron donor compared to ligands l-b and l-c. the results of qtaim, nocv and nbo suggest that the am-n bonds in the studied complexes have more covalent character compared to the eu-n bonds. based on the thermodynamic analysis, [m(no3)(h2o)(8)](2+) + l + 2no(3)(-) = [ml(no3)(3)] + 8h(2)o should be the most probable reaction in the solvent extraction system. our results clearly verify that the relatively harder oxygen atoms offer these ligands higher coordination affinities toward both of the an(iii) and ln(iii) ions compared to the relatively softer nitrogen atoms. however, the latter possess stronger affinities toward an(iii) over ln(iii), which partly results in the selectivity of these ligands. this work can afford useful information on achieving efficient an(iii)/ln(iii) separation through tuning the structural rigidity and hardness or softness of the functional moieties of the ligands. |
| WOS关键词 | ACTINIDE-LANTHANIDE SEPARATION ; ELECTRON-DENSITY DISTRIBUTION ; SEGMENTED CONTRACTION SCHEME ; PSEUDOPOTENTIAL BASIS-SETS ; TRANSITION-STATE METHOD ; TRIVALENT ACTINIDE ; FUNCTIONAL THEORY ; IONIC-RADII ; COMPLEXES ; ENERGY |
| WOS研究方向 | Chemistry ; Physics |
| WOS类目 | Chemistry, Physical ; Physics, Atomic, Molecular & Chemical |
| 语种 | 英语 |
| WOS记录号 | WOS:000412763700051 |
| 出版者 | ROYAL SOC CHEMISTRY |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2177117 |
| 专题 | 高能物理研究所 |
| 通讯作者 | Shi, Wei-Qun |
| 作者单位 | 1.Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China 2.Chinese Acad Sci, Inst High Energy Phys, Key Lab Biomed Effects Nanomat & Nanosafety, Beijing 100049, Peoples R China 3.Capital Normal Univ, Dept Chem, Beijing 100048, Peoples R China 4.Soochow Univ, Sch Radiol & Interdisciplinary Sci RAD X, Suzhou 215123, Peoples R China 5.Soochow Univ, Collaborat Innovat Ctr Radiat Med, Jiangsu Higher Educ Inst, Suzhou 215123, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wu, Qun-Yan,Song, Yu-Ting,Ji, Lin,et al. Theoretically unraveling the separation of am(iii)/eu(iii): insights from mixed n,o-donor ligands with variations of central heterocyclic moieties[J]. Physical chemistry chemical physics,2017,19(39):26969-26979. |
| APA | Wu, Qun-Yan,Song, Yu-Ting,Ji, Lin,Wang, Cong-Zhi,Chai, Zhi-Fang,&Shi, Wei-Qun.(2017).Theoretically unraveling the separation of am(iii)/eu(iii): insights from mixed n,o-donor ligands with variations of central heterocyclic moieties.Physical chemistry chemical physics,19(39),26969-26979. |
| MLA | Wu, Qun-Yan,et al."Theoretically unraveling the separation of am(iii)/eu(iii): insights from mixed n,o-donor ligands with variations of central heterocyclic moieties".Physical chemistry chemical physics 19.39(2017):26969-26979. |
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