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Ashfaq Afsar

Covalent Immobilization of Minor Actinide-Selective Ligands onto Magnetic Nanoparticles 9 September 2015 UK-Korea Nuclear Consortium Kick-Off Meeting. Ashfaq Afsar

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Ashfaq Afsar

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  1. Covalent Immobilization of Minor Actinide-Selective Ligands onto Magnetic Nanoparticles9 September 2015UK-Korea Nuclear Consortium Kick-Off Meeting Ashfaq Afsar Petr Distler, Chad Edwards, Andreas Geist, Laurence M. Harwood, Mark E. Hodson, Michael J. Hudson, Jan John, Dominic M. Laventine, Elizabeth J. Shaw, Clint Sharrad, James Westwood, Roger Whitehead.

  2. Ligands Immobilized on Magnetic Nanoparticles Liquid-liquid extraction Immobilized ligands • Efficient separation of particles • Requires substantial tankage and • reagents • Simple, versatile and compact • Generates significant quantities of • secondary waste • Minimized secondary waste • Suitable for low concentrations • (legacy wastes) • Not suitable for low concentrations • Good kinetics

  3. Ligands Immobilized on Magnetic Nanoparticles Nanoparticles extracted on application of magnetic field. Nanoparticles dispersed in water (colloidal solution).

  4. Core-shell MNPs synthesis A. Afsar, L. M. Harwood, M. J. Hudson, M. E. Hodson and E. J. Shaw, Chem. Comm., 2014, 50, 7477–7480.

  5. Immobilisation of Neocuproine A. Afsar, L. M. Harwood, M. J. Hudson, M. E. Hodson and E. J. Shaw, Chem. Comm., 2014, 50, 7477–7480.

  6. Extraction Results 12 ppm of Cu(II) solutions (12 mL) 12 mg of MNPs Shaking at 2500/min Separated by neodymium magnet A. Afsar, L. M. Harwood, M. J. Hudson, M. E. Hodson and E. J. Shaw, Chem. Comm., 2014, 50, 7477–7480.

  7. Synthesis of Br-CyMe4-BTPhen F. W. Lewis, L. M. Harwood, M. J. Hudson et al., J. Am. Chem. Soc.,2011, 133(33), 13093-13102. D. M. Laventine, A. Afsar, M. J. Hudson and L. M. Harwood, Heterocycles, 2012, 86(2), 1419-1429. A. Afsar, D. M. Laventine, L. M. Harwood, M. J. Hudson and A. Geist, Chem. Commun., 2013, 49, 8534-8536.

  8. Immobilisation of C1-BTPhen 241Am(III) + 152Eu(III) in HNO3 of varied concentrations +18 mg of MNPs Sonication time (10 min),shaking at 1800/min (90 min), separated by centrifugation (10 min) 15-20% extraction observed But lack of selectivity A. Afsar, D. M. Laventine, L. M. Harwood, M. J. Hudson and A. Geist, Heterocycles, 2014, 88(1), 613-620.

  9. Immobilisation of CyMe4-BTPhen A. Afsar,L. M. Harwood, M. J. Hudson, P. Distler and J. John, Chem. Comm., 2014, 50, 15082–15085.

  10. Extraction Results 241Am(III) + 152Eu(III) + 244Cm(III) in HNO3 of varied concentrations +18 mg of MNPs Sonication time (10 min),shaking at 1800/min (90 min), separated by centrifugation (10 min) At 0.001 M HNO3, D > 700 for both Am(III) and Eu(III), but no significant selectivity (SFAm/Eu = 1.7) At 4 M HNO3, DEu ~ 0, excellent selectivity (SFAm/Eu > 1600) A. Afsar,L. M. Harwood, M. J. Hudson, P. Distler and J. John, Chem. Comm., 2014, 50, 15082–15085.

  11. Screening Results Ligand in 1-octanol (0.01 M) 241Am(III) + 152Eu(III) + 244 Cm(III) in HNO3 of varied concentrations Contact time = 60 mins at 22 oC DAm = ca. 335, DEu = ca. 5 SFAm/Eu = ca. 70 at 3 M HNO3 DAm = ca. 1581, DEu = ca. 5 SFAm/Eu = ca. 320 at 3 M HNO3 A. Afsar, L. M. Harwood, M. J. Hudson, A. Geist and J. Westwood, Chem. Commun., 2015, 51, 5860 – 5863.

  12. Am(III)/Cm(III) Separation max SFAm/Cm = ca. 7 at 0.1 M HNO3 max SFAm/Cm = ca. 5 at 1 M HNO3 A. Afsar, L. M. Harwood, M. J. Hudson, A. Geist and J. Westwood, Chem. Commun., 2015, 51, 5860 – 5863.

  13. Modified Silica Gels Sigma-Aldrich 364258–50 G = £193 Sigma-Aldrich 364266–50 G = £124

  14. Modified Silica Gels

  15. Achievements and Conclusions Iron oxide (Fe2O3) MNPs coated with silica and functionalized with CyMe4-BTPhen have the ability to extract various metal ions from aqueous solution probably as 1:1 (metal:ligand complexes), leading to a totally new extraction profile compared to liquid-liquid extraction systems. Adding substituents to the phenanthroline backbone at the 5- and 5,6-positions of BTPhens, enable these ligands to be fine-tuned in order to enhance the selectivity of Am(III) from Ln(III) and Cm(III). This has opened up a whole new range of extraction possibilities leading to very high Am3+ – Eu3+ and workable Am3+ – Cm3+ separations that are dependent upon nitric acid concentration.

  16. Acknowledgments Chemistry group Laurence Harwood Michael Hudson AshfaqAfsar Joe Cowell James Westwood Soil science group Mark Hodson Liz Shaw David Hughes Extraction studies group Andreas Geist (KIT-INE Karlsruhe) Jan John (CTU Prague) Petr Distler(CTU Prague) UCLan Gary Bond Harry Eccles Supporting staff Peter Harris (TEM) Peter Health (NMR) Martin Reeves (MS) Ogla Khutoryanskaya (TGA) Michael Andrews (XRD) Anne Dudley (AA)

  17. OK dragon! Come out of that cave and fight!!

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