Design criteria for tetradentate phenanthroline-derived heterocyclic ligands to separate Am(III) from Eu(III)

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• 作者：ChengLiang Xiao (1)
  QunYan Wu (1)
  CongZhi Wang (1)
  YuLiang Zhao (1)
  ZhiFang Chai (1) (2)
  WeiQun Shi (1)
  
• 关键词：minor actinide ; lanthanide ; phenanthroline ; separation ; DFT
• 刊名：SCIENCE CHINA Chemistry
• 出版年：2014
• 出版时间：November 2014
• 年：2014
• 卷：57
• 期：11
• 页码：1439-1448
• 全文大小：1,012 KB
• 参考文献：1. Panak PJ, Geist A. Complexation and extraction of trivalent actinides and lanthanides by triazinylpyridine N-donor ligands. / Chem Rev, 2013, 113: 1199-236 CrossRef
  2. Hudson MJ, Harwood LM, Laventine DM, Lewis FW. Use of soft heterocyclic N-donor ligands to separate actinides and lanthanides. / Inorg Chem, 2013, 52: 3414-428 CrossRef
  3. Hancock RD. The pyridyl group in ligand design for selective metal ion complexation and sensing. / Chem Soc Rev, 2013, 42: 1500-524 CrossRef
  4. Modolo G, Wilden A, Geist A, Magnusson D, Malmbeck R. A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate. / Radiochim Acta, 2012, 100: 715-25 CrossRef
  5. Lan JH, Shi WQ, Yuan LY, Li J, Zhao YL, Chai ZF. Recent advances in computational modeling and simulations on the An(III)/Ln(III) separation process. / Coord Chem Rev, 2012, 256: 1406-17 CrossRef
  6. Cao X, Heidelberg D, Ciupka J, Dolg M. First-principles study of the separation of Am(III)/Cm(III) from Eu(III) with Cyanex 301. / Inorg Chem, 2010, 49: 10307-0315 CrossRef
  7. Kolarik Z. Complexation and separation of lanthanides(III) and actinides(III) by heterocyclic N-donors in solutions. / Chem Rev, 2008, 108: 4208-252 CrossRef
  8. Chen J, Zhu YJ, Jiao RZ. The separation of Am from lanthanides by purified Cyanex 301 extraction. / Sep Sci Technol, 1996, 31: 2723-731 CrossRef
  9. Nash KL, Choppin GR. Separations chemistry for actinide elements: recent developments and historical perspective. / Sep Sci Technol, 1997, 32: 255-74 CrossRef
  10. Kolarik Z, Mullich U, Gassner F. Extraction of Am(III) and Eu(III) nitrates by 2,6-di-(5,6-dipropyl-1,2,4-triazin-3-yl)pyridines. / Solv Extr Ion Exch, 1999, 17: 1155-170 CrossRef
  11. Kolarik Z, Mullich U, Gassner F. Selective extraction of Am(III) over Eu(III) by 2,6-ditriazolyl- and 2,6-ditriazinylpyridines. / Solv Extr Ion Exch, 1999, 17: 23-2 CrossRef
  12. Trumm S, Geist A, Panak PJ, Fangh?nel T. An improved hydrolytically-stable bis-triazinyl-pyridine (BTP) for selective actinide extraction. / Solv Extr Ion Exch, 2011, 29: 213-29 CrossRef
  13. Usuda S, Wei YZ, Liu RQ, Li Z, Xu YL, Wu Y, Kim S. Challenges to develop single-column MA(III) separation from HLLW using R-BTP type adsorbents. / Sci China Chem, 2012, 55: 1732-738 CrossRef
  14. Wei YZ, Wang XP, Liu RQ, Wu Y, Usuda S, Arai T. An advanced partitioning process for key elements separation from high level liquid waste. / Sci China Chem, 2012, 55: 1726-731 CrossRef
  15. Banik NL, Denecke MA, Geist A, Modolo G, Panak PJ, Rothe J. 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)-pyridine: structures of An(III) and Ln(III) 1:3 complexes and selectivity. / Inorg Chem Commun, 2013, 29: 172-74 CrossRef
  16. Foreman MRS, Hudson MJ, Drew MGB, Hill C, Madic C. Complexes formed between the quadridentate, heterocyclic molecules 6,6-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2-bipyridine (BTBP) and lanthanides(III): implications for the partitioning of actinides(III) and lanthanides(III). / Dalton Trans, 2006: 1645-653
  17. Lan JH, Shi WQ, Yuan LY, Zhao YL, Chai ZF. Trivalent ac
• 作者单位：ChengLiang Xiao (1)
  QunYan Wu (1)
  CongZhi Wang (1)
  YuLiang Zhao (1)
  ZhiFang Chai (1) (2)
  WeiQun Shi (1)
  
  1. Key Laboratory of Nuclear Radiation and Nuclear Energy Technology; Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China
  2. School of Radiological and Interdisciplinary Sciences, Soochow University, Suzhou, 215123, China
  
• ISSN：1869-1870

文摘

To design novel phenanthroline-derived soft ligands for selectively separating minor actinides from lanthanides, four tetradentate phenanthroline-derived heterocyclic ligands (BTPhen, BPyPhen, BPzPhen, and BBizPhen) were constructed and their complexation behaviors with Am(III) and Eu(III) were systematically investigated by density functional theory (DFT) coupled with relativistic small-core pseudopotential. In all the 1:1-type species, the metal ion is in the center of the cavity and coordinates with two nitrogen atoms (N1 and N1- of the phenanthroline skeleton and the other two nitrogen atoms (N2 and N2- of the auxiliary groups. The bond lengths of Am-N are comparable to or even shorter than those of Eu-N bonds because the ionic radii of Am(III) are larger than those of Eu(III). Additionally, the negative ΔΔG Am/Eu value for the reaction of [M(H2O)4(NO3)3] + L ?ML(NO3)3 + 4H2O indicates that the complexation reaction of Am(III) is more energetically favorable than that of Eu(III); this can be considered as an important design criterion to screen phenanthroline-derived ligands for MA(III) extraction. According to this criterion, the selectivity of tetradentate phenanthroline-derived ligands for separating Am(III) over Eu(III) follows the order of BTPhen > BBizPhen > BPyPhen > BPzPhen.