Understanding Am3+/Cm3+ separation with H4TPAEN and its hydrophilic derivatives: a quantum chemical study

被引:26
|
作者
Huang, Pin-Wen [1 ,2 ,3 ]
Wang, Cong-Zhi [1 ,2 ]
Wu, Qun-Yan [1 ,2 ]
Lan, Jian-Hui [1 ,2 ]
Song, Gang [4 ]
Chai, Zhi-Fang [1 ,2 ,5 ,6 ]
Shi, Wei-Qun [1 ,2 ]
机构
[1] Chinese Acad Sci, Lab Nucl Energy Chem, Inst High Energy Phys, Beijing 100049, Peoples R China
[2] Chinese Acad Sci, Key Lab Biomed Effects Nanomat & Nanosafety, Inst High Energy Phys, Beijing 100049, Peoples R China
[3] Zhejiang Univ Water Resources & Elect Power, Hangzhou 310018, Zhejiang, Peoples R China
[4] Guangdong Prov Key Lab Radionuclides Pollut Contr, Guangzhou 510006, Guangdong, Peoples R China
[5] Soochow Univ, Sch Radiol & Interdisciplinary Sci RAD X, Suzhou 215123, Peoples R China
[6] Soochow Univ, Collaborat Innovat Ctr Radiat Med, Jiangsu Higher Educ Inst, Suzhou 215123, Peoples R China
基金
国家自然科学基金重大项目; 中国博士后科学基金; 中国国家自然科学基金;
关键词
SELECTIVE AM(III) SEPARATION; SOLVENT-EXTRACTION; DIGLYCOLAMIDE TODGA; LANTHANIDE CATIONS; MINOR ACTINIDES; HARTREE-FOCK; DENSITY; COMPLEXATION; ENERGY; EU(III);
D O I
10.1039/c7cp08441b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Am3+/Cm3+ separation is an extremely hard but important task in nuclear waste treatment. In this study, Am and Cm complexes formed with a back-extraction agent N,N,N,N-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H(4)TPAEN) and its two derivatives with hydrophilic substituents (methoxy and morpholine groups) were investigated using the density functional theory (DFT). The optimized geometrical structures indicated that the Am3+ cation matched better with the cavities of the three studied ligands than Cm3+, and the Am3+ cations were located deeper in the cavities of the ligands. The bond order and quantum theory of atoms in molecules (QTAIM) analyses suggested that ionic interactions dominated An-N and An-O (An = Cm and Am) bonds. However, weak and different extents of partial covalency could also be found in the Am-N and Cm-N bonds. The O donor atoms in the carboxylate groups preferably coordinated with Cm3+ rather than Am3+, whereas the N atoms preferred Am3+. Therefore, the Am3+/Cm3+ selectivity of H(4)TPAEN and its two hydrophilic derivatives may be ascribed to the competition between the An-N and An-O interactions and the few dissimilarities in their geometrical structures. Based on our calculations, the methoxy and morpholine groups in the two derivatives can serve as electron-donating groups and enhance the strength of the An-N-PY bonds (N-PY denotes the nitrogen atom of pyridine ring). When compared with the Am-complex, the Cm-complex exhibited significant strength effect, resulting in the relatively lower Am3+/Cm3+ separation ability of the H(4)TPAEN's hydrophilic derivatives.
引用
收藏
页码:14031 / 14039
页数:9
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