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Download Author Version (PDF) Dalton Transactions Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/dalton Page 1 of 20 Dalton Transactions The structures of CyMe 4-BTBP complexes of americium(III) and europium(III) in solvents used in solvent extraction, explaining their separation properties Christian Ekberg, a,* Elin Löfström-Engdahl,a Emma Aneheim,a Mark R.StJ.Foreman,a Andreas Geist, b Daniel Lundberg,c Melissa Denecke, d and Ingmar Persson c,* a Nuclear Chemistry / Industrial materials recycling, Chalmers University of Technology, SE-412 96 Göteborg, Sweden. E-mail: [email protected] b Karlsruhe Institute of Technology, Institute for Nuclear Waste Disposal (INE), Manuscript 76021 Karlsruhe, Germany. c Department of Chemistry and Biotechnology, Uppsala Biocenter, Swedish University of Agricultural Sciences, P.O. Box 7015, SE-750 07 Uppsala, Sweden. E-mail: [email protected] Accepted d Dalton Nuclear Institute, The University of Manchester, Manchester M13 9PL, United Kingdom. † Electronic supplementary information (ESI) available: Description of conductivity measurements performed. See DOI: 10.1039/c4dt0xxxxx Transactions Dalton - 1 - Dalton Transactions Page 2 of 20 Graphical abstract The structure around the absorbing atom in the dicomplexes of 6,6’-bis(5,5,8,8-tetramethyl- 5,6,7,8-tetrahydro-benzo[1,2,4]triazin-3-yl)[2,2]bipyridine, CyMe 4-BTBP, with americium(III) and europium(III) have been determined by means of Am and Eu L 3 edge EXAFS spectroscopy in a series of solvents used to separate these metal ions using solvent extraction. The obtained structural information has been correlated with previously reported solubility and selectivity data as well as ionic radii in general terms. Manuscript Accepted Transactions Dalton - 2 - Page 3 of 20 Dalton Transactions Abstract Separation of trivalent actinoid (An(III)) and lanthanoid (Ln(III)) ions is extremely challenging due to their similar ionic radii and chemical properties. Poly-aromatic nitrogen compounds acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(III) from Ln(III). One of these compounds, 6,6’- bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzol[1,2,4]triazin-3-yl)[2,2]bipyridine, CyMe 4- BTBP, has proven to be resistant towards acidic environments and strong radiation from radioactive decomposition. EXAFS studies of the dicomplexes of CyMe 4-BTBP with americium(III) and europium(III) in nitrobenzene, cyclohexanone, 1-hexanol, 1-octanol and malonamide (DMDOHEMA) in 1-octanol have been carried out to get a deeper understanding of the parameters responsible for the separation. The predominating complexes 2+ 3+ independent of solvent used are [Am(CyMe 4-BTBP) 2(NO 3)] and [Eu(CyMe 4-BTBP) 2] , Manuscript respectively, which are present as outer-sphere ion-pairs with nitrate ions in the studied solvents with low relative permittivity. The presence of a nitrate ion in the first coordination sphere of the americium(III) complex compensates the charge density of the complex considerably in comparison when only outer-sphere ion-pairs are formed as for the 3+ [Eu(CyMe 4-BTBP) 2] complex. The stability and solubility of a complex in a solvent with low relative permittivity increase with decreasing charge density. The [Am(CyMe 4- Accepted 2+ BTBP) 2(NO 3)] complex will therefore be increasingly soluble and stabilized over the 3+ [Eu(CyMe 4-BTBP) 2] complex in solvents with decreasing relative permittivity of the solvent. The separation of americium(III) from europium(III) with CyMe 4-BTBP as extraction agent will increase with decreasing relative permittivity of the solvent, and thereby also with decreasing solubility of CyMe 4-BTBP. The choice of solvent is therefore a balance of a high separation factor and sufficient solubility of the CyMe 4-BTBP ligand. Transactions Dalton - 3 - Dalton Transactions Page 4 of 20 Introduction Approximately 12% of all electric energy in the world stems from nuclear power.1 Today the utilisation of nuclear power is an effective way to produce electricity with very low emission of greenhouse gases,2 which has increased the interest for the technique. However, a concern with nuclear power is the production of highly radioactive used nuclear fuel (UNF). The UNF is highly radiotoxic to mankind and the environment, and will continue to be so for a very long time due to the long life-times of several isotopes.3 Some countries (UK, France, Russia, Japan, India) complement direct disposal of commercial UNF in deep underground geologic repositories by UNF reprocessing, whereby uranium and plutonium are reused or recycled as nuclear fuel. The associated highly radioactive waste from reprocessing, including fission products and the minor actinoids neptunium, americium and curium, is vitrified for ultimate Manuscript disposal in a deep geologic repository. A future component in UNF handling is transmutation of the minor actinoids into less radiotoxic or less stable isotopes. By transmuting the actinoids, the waste volume, long-term heat load and radiotoxicity of the highly radioactive waste can be reduced significantly.4-6 However, before their transmutation the actinoids must be separated from the UNF fission, corrosion and activation products. One way to achieve the required separation is through solvent extraction. Accepted Separation of trivalent actinoid (An(III)) and lanthanoid (Ln(III)) ions represents one of the most challenging separations due to their similar ionic radii and chemical properties. Recent studies have shown that poly-aromatic nitrogen compounds, N-PAHs, acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(III) from Ln(III).7-10 One of these N-PAHs, 6,6’-bis(5,5,8,8-tetramethyl-5,6,7,8- tetrahydro-benzol[1,2,4]triazin-3-yl)[2,2]bipyridine, CyMe 4-BTBP (Scheme 1), has promising process potential, 11-16 as it has proven to be resistant towards acidic Transactions environments17-19 and strong radiation from radioactive decomposition 13,20 present at the separation process of actinoids from UNF. CyMe 4-BTBP extracts An(III) and Ln(III) from concentrated nitric acid or nitrate solutions to the organic phase by a complex formation 18,21 (3-n)+ mechanism of predominantly 1:2 complexes, [M(CyMe 4-BTBP) 2(NO 3)n(solv) m] , as Dalton does the structurally similar 6,6’-bis(5,6-dipentyl-[1,2,4]triazin-3-yl)-[2,2’]-bipyridine (C5- BTBP) molecule, see Eq. 1.22,23 3+ − (3-n)+ − M aq + 3 NO 3 aq + 2 BTBP org {[M(BTBP) 2(NO 3)n(solv) m] ···(NO 3 )3-n}org (Eq. 1) - 4 - Page 5 of 20 Dalton Transactions The 1:2 stoichiometry has been confirmed for different metals by electrospray ionisation mass spectrometry (ESI-MS), time-resolved laser-induced fluorescence spectroscopy (TRLFS), and extended X-ray absorption fine structure (EXAFS) in solution.24-29 In the solid state, structures with both 1:1 and 1:2 stoichiometry have been reported. 17,27,28,30,31 Complexes with 1:2 stoichiometry may have different number of nitrate ions bound to the central metal ion depending on the experimental conditions during preparation; 3+ 24,25 2+ 24,28,29,31 3+ 25,26,28 [M(BTBP) 2] , [M(BTBP) 2(NO 3)] , or [M(BTBP) 2(H 2O) n] . Qualitative reasoning concerning the Lewis basicity of the extractant and the somewhat softer character of the actinoid(III) ions compared to the lanthanoid(III) ones has been used to explain the An(III)/Ln(III) separation capacity of N-PAH ligands.32,33 An(III)/Ln(III) separa- 18,34,35 tion by CyMe 4-BTBP has also been observed to vary with the solvent used. In order to Manuscript understand the fundamental basis for An(III)/Ln(III) separation properties of BTBP ligands, the speciation in detail, and the role of the solvent, EXAFS studies of these complexes have been carried out in solution. Analysis of EXAFS data gives information about the distances to the surrounding atoms which can be used to determine the structural environment around the absorbing atom and thereby the speciation in solution which may differ from the one in the solid state. In this study the americium(III) and europium(III) CyMe 4-BTBP complexes have Accepted been studied in selected solvents previously investigated for their potential in separation processes including nitrobenzene, cyclohexanone, 1-hexanol, and 1-octanol.12,24,36,37 Transactions Scheme 1. Molecular structure of 6,6’-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzol[1,2,4]triazin- 3-yl)[2,2]bipyridine, CyMe 4-BTBP (left), and a graphical representation of the EXAFS single scattering pathways between a metal ion and one CyMe 4-BTBP ligand (right): M-N [dark grey], M⋅⋅⋅ C’ [grey] and M⋅⋅⋅ C” [light grey], where the two latter include six carbon and two nitrogen atoms Dalton per ligand, respectively.
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