Insight into the extraction mechanism of americium(iii) over europium(iii) with pyridylpyrazole: a relativistic quantum chemistry study
文献类型：期刊论文
| 作者 | Kong, Xiang-He1,2; Wu, Qun-Yan1; Wang, Cong-Zhi1; Lan, Jian-Hui1; Chai, Zhi-Fang1,3,4; Nie, Chang-Ming2; Shi, Wei-Qun1 |
| 刊名 | Journal of physical chemistry a
 |
| 出版日期 | 2018-05-10 |
| 卷号 | 122期号:18页码:4499-4507 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/acs.jpca.8b00177 |
| 通讯作者 | Shi, wei-qun(shiwq@ihep.ac.cn) |
| 英文摘要 | Separation 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. |
| WOS关键词 | DENSITY-FUNCTIONAL THEORY ; SEGMENTED CONTRACTION SCHEME ; PSEUDOPOTENTIAL BASIS-SETS ; ACTINIDE(III)/LANTHANIDE(III) SEPARATION ; SELECTIVE EXTRACTION ; ELECTRONIC-STRUCTURE ; TRIVALENT ACTINIDE ; COMPLEXES ; LANTHANIDE ; LIGANDS |
| 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:000432204200014 |
| 出版者 | AMER CHEMICAL SOC |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2177556 |
| 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.Univ South China, Sch Nucl Resources Engn, Hengyang 421001, Peoples R China 3.Soochow Univ, Sch Radiol & Interdisciplinary Sci RAD X, Suzhou 215123, Peoples R China 4.Soochow Univ, Collaborat Innovat Ctr Radiat Med Jiangsu Higher, Suzhou 215123, Peoples R China |
| 推荐引用方式 GB/T 7714 | Kong, Xiang-He,Wu, Qun-Yan,Wang, Cong-Zhi,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 | Kong, Xiang-He.,Wu, Qun-Yan.,Wang, Cong-Zhi.,Lan, Jian-Hui.,Chai, Zhi-Fang.,...&Shi, Wei-Qun.(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 | Kong, Xiang-He,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. |
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