Spectroscopic investigation of the different complexation and extraction properties of diastereomeric diglycolamide ligands
-
Patrik Weßling
,
Michael Trumm
Abstract
(2R,2′S)-2,2′-oxybis-(N,N-didecylpropanamide) (cis-mTDDGA) and (2R,2′R)-2,2′-oxybis-(N,N-didecylpropanamide) (trans-mTDDGA) were studied using time-resolved laser fluorescence spectroscopy (TRLFS), vibronic side-band spectroscopy (VSBS) and density functional theory calculations (DFT) to find reasons for their different extraction properties. Stability constants of the respective Cm(III) and Eu(III) complexes show cis-mTDDGA to be the superior ligand which is in agreement with results from extraction experiments. cis-mTDDGA extracts Cm(III) and Eu(III) as 1:3 complexes. In case of trans-mTDDGA, 1:2 complexes of the form [M(trans-mTDDGA)2(η1-NO3)(H2O)2]2+ (M = Cm, Eu) are extracted additionally to the 1:3 complexes. VSBS and DFT confirm the presence of inner-sphere nitrate in the 1:2 complex.
Funding source: European Research Council http://dx.doi.org/10.13039/501100000781
Award Identifier / Grant number: 755171
Funding source: German Federal Ministry for Research and Education
Award Identifier / Grant number: 02NUK059A
Award Identifier / Grant number: 02NUK059C
-
Author contributions: All authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
-
Research funding: This work has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (project GENIORS, grant agreement no. 755171) and the German Federal Ministry for Research and Education (grant agreement no. 02NUK059A, 02NUK059C).
-
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
1. Sasaki, Y., Sugo, Y., Suzuki, S., Tachimori, S. The novel extractants, diglycolamides, for the extraction of lanthanides and actinides in HNO3/n-dodecane system. Solvent Extr. Ion Exch. 2001, 19, 91. https://doi.org/10.1081/sei-100001376.Suche in Google Scholar
2. Ansari, S. A., Pathak, P., Mohapatra, P. K., Manchanda, V. K. Chemistry of diglycolamides: promising extractants for actinide partitioning. Chem. Rev. 2012, 112, 1751. https://doi.org/10.1021/cr200002f.Suche in Google Scholar PubMed
3. Whittaker, D., Geist, A., Modolo, G., Taylor, R., Sarsfield, M., Wilden, A. Applications of diglycolamide based solvent extraction processes in spent nuclear fuel reprocessing, part 1: TODGA. Solvent Extr. Ion Exch. 2018, 36, 223. https://doi.org/10.1080/07366299.2018.1464269.Suche in Google Scholar
4. Taylor, R., Ed. Reprocessing and Recycling of Spent Nuclear Fuel; Woodhead Publishing: Cambridge, UK, 2015.Suche in Google Scholar
5. Bhattacharyya, A., Mohapatra, P. K. Separation of trivalent actinides and lanthanides using various ‘N’, ‘S’ and mixed ‘N, O’ donor ligands: a review. Radiochim. Acta 2019, 107, 931. https://doi.org/10.1515/ract-2018-3064.Suche in Google Scholar
6. Baron, P., Cornet, S. M., Collins, E. D., DeAngelis, G., Del Cul, G., Fedorov, Y., Glatz, J. P., Ignatiev, V., Inoue, T., Khaperskaya, A., Kim, I. T., Kormilitsyn, M., Koyama, T., Law, J. D., Lee, H. S., Minato, K., Morita, Y., Uhlíř, J., Warin, D., Taylor, R. J. A review of separation processes proposed for advanced fuel cycles based on technology readiness level assessments. Prog. Nucl. Energy 2019, 117, 103091. https://doi.org/10.1016/j.pnucene.2019.103091.Suche in Google Scholar
7. Geist, A., Adnet, J.-M., Bourg, S., Ekberg, C., Galán, H., Guilbaud, P., Miguirditchian, M., Modolo, G., Rhodes, C., Taylor, R. An overview of solvent extraction processes developed in Europe for advanced nuclear fuel recycling, part 1 – heterogeneous recycling. Separ. Sci. Technol. 2021, 56, 1866. https://doi.org/10.1080/01496395.2020.1795680.Suche in Google Scholar
8. Wilden, A., Kreft, F., Schneider, D., Paparigas, Z., Modolo, G., Lumetta, G. J., Gelis, A. V., Law, J. D., Geist, A. Counter current actinide lanthanide separation process (ALSEP) demonstration test with a simulated PUREX raffinate in centrifugal contactors on the laboratory scale. Appl. Sci. 2020, 10, 7217. https://doi.org/10.3390/app10207217.Suche in Google Scholar
9. OECD-NEA. Homogeneous Versus Heterogeneous Recycling of Transuranics in Fast Nuclear Reactors, in NEA No. 7077; Nuclear Energy Agency (NEA): Paris, 2012.Suche in Google Scholar
10. Miguirditchian, M., Chareyre, L., Hérès, X., Hill, C., Baron, P., Masson, M. GANEX: adaptation of the DIAMEX-SANEX process for the group actinide separation. In Proceedings of the International Conference on GLOBAL 2007 (Advanced Nuclear Fuel Cycles and Systems), Boise, Idaho, USA, 9–13 September, 2007.Suche in Google Scholar
11. Miguirditchian, M., Roussel, H., Chareyre, L., Baron, P., Espinoux, D., Calor, J.-N., Viallesoubranne, C., Lorrain, B., Masson, M. HA demonstration in the Atalante facility of the GANEX 2nd cycle for the grouped TRU extraction. In Proceedings of the International Conference on GLOBAL 2009 (The Nuclear Fuel Cycle: Sustainable Options & Industrial Perspectives), Paris, France, 6–11 September, 2009.Suche in Google Scholar
12. Carrott, M., Geist, A., Hérès, X., Lange, S., Malmbeck, R., Miguirditchian, M., Modolo, G., Wilden, A., Taylor, R. Distribution of plutonium, americium and interfering fission products between nitric acid and a mixed organic phase of TODGA and DMDOHEMA in kerosene, and implications for the design of the “EURO-GANEX” process. Hydrometallurgy 2015, 152, 139. https://doi.org/10.1016/j.hydromet.2014.12.019.Suche in Google Scholar
13. Carrott, M., Bell, K., Brown, J., Geist, A., Gregson, C., Hérès, X., Maher, C., Malmbeck, R., Mason, C., Modolo, G., Müllich, U., Sarsfield, M., Wilden, A., Taylor, R. Development of a new flowsheet for co-separating the transuranic actinides: the “EURO-GANEX” process. Solvent Extr. Ion Exch. 2014, 32, 447. https://doi.org/10.1080/07366299.2014.896580.Suche in Google Scholar
14. Malmbeck, R., Magnusson, D., Bourg, S., Carrott, M., Geist, A., Hérès, X., Miguirditchian, M., Modolo, G., Müllich, U., Sorel, C., Taylor, R., Wilden, A. Homogenous recycling of transuranium elements from irradiated fast reactor fuel by the EURO-GANEX solvent extraction process. Radiochim. Acta 2019, 107, 917. https://doi.org/10.1515/ract-2018-3089.Suche in Google Scholar
15. Wilden, A., Modolo, G., Lange, S., Sadowski, F., Beele, B. B., Skerencak-Frech, A., Panak, P. J., Iqbal, M., Verboom, W., Geist, A., Bosbach, D. Modified diglycolamides for the An(III) + Ln(III) co-separation: evaluation by solvent extraction and time-resolved laser fluorescence spectroscopy. Solvent Extr. Ion Exch. 2014, 32, 119. https://doi.org/10.1080/07366299.2013.833791.Suche in Google Scholar
16. Klaß, L., Wilden, A., Kreft, F., Wagner, C., Geist, A., Panak, P. J., Herdzik-Koniecko, I., Narbutt, J., Modolo, G. Evaluation of the hydrophilic complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its methyl-substituted analogues in the selective Am(III) separation. Solvent Extr. Ion Exch. 2019, 37, 297.10.1080/07366299.2019.1651039Suche in Google Scholar
17. Malmbeck, R., Magnusson, D., Geist, A. Modified diglycolamides for grouped actinide separation. J. Radioanal. Nucl. Chem. 2017, 314, 2531. https://doi.org/10.1007/s10967-017-5614-2.Suche in Google Scholar
18. Wilden, A., Kowalski, P. M., Klaß, L., Kraus, B., Kreft, F., Modolo, G., Li, Y., Rothe, J., Dardenne, K., Geist, A., Leoncini, A., Huskens, J., Verboom, W. Unprecedented inversion of selectivity and extraordinary difference in the complexation of trivalent f-elements by diastereomers of a methylated diglycolamide. Chem. Eur J. 2019, 25, 5507. https://doi.org/10.1002/chem.201806161.Suche in Google Scholar PubMed
19. Verlinden, B., Wilden, A., Van Hecke, K., Egberink, R. J. M., Huskens, J., Verboom, W., Hupert, M., Weßling, P., Geist, A., Panak, P. J., Hermans, R., Verwerft, M., Modolo, G., Binnemanns, K., Cardineals, T. Solvent Extr. Ion Exch. (submitted).Suche in Google Scholar
20. Iqbal, M., Huskens, J., Verboom, W., Sypula, M., Synthesis, M. G. Supramol. Chem. 2010, 22, 827. https://doi.org/10.1080/10610278.2010.506553.Suche in Google Scholar
21. Lee, C., Yang, W., Parr, R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785. https://doi.org/10.1103/physrevb.37.785.Suche in Google Scholar PubMed
22. Weigend, F., Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297. https://doi.org/10.1039/b508541a.Suche in Google Scholar PubMed
23. TURBOMOLE V7.0. A Development of University of Karlsruhe and Forschungszentrum KarlsruheGmbH; TURBOMOLE GmbH, 1989–2007. Since 2007 http://www.turbomole.com.Suche in Google Scholar
24. Küchle, W., Dolg, M., Stoll, H., Preuss, H. Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide. J. Chem. Phys. 1994, 100, 7535.10.1063/1.466847Suche in Google Scholar
25. Ishimori, K., Watanabe, M., Kimura, T., Yaita, T., Yamada, T., Kataoka, Y., Shinoda, S., Tsukube, H. Novel separation system of trivalent actinides – combined effects of substituted tris(2-pyridylmethyl)amine ligand and hydrophobic counter-anion. Chem. Lett. 2005, 34, 1112. https://doi.org/10.1246/cl.2005.1112.Suche in Google Scholar
26. Lemaire, M., Guy, A., Chomel, R., Foos, J. Dicyclohexano-18-crown-6 ether: a new selective extractant for nuclear fuel reprocessing. J. Chem. Soc., Chem. Commun. 1991, 1152. https://doi.org/10.1039/c39910001152.Suche in Google Scholar
27. Tsaryuk, V. I., Savchenko, V. D., Aryutkina, N. L., Chenskaya, T. B. Vibronic spectra of europium nitrate hexahydrate. J. Appl. Spectrosc. 1994, 60, 185. https://doi.org/10.1007/bf02606351.Suche in Google Scholar
28. Tsaryuk, V. I., Savchenko, V. D., Zolin, V. F., Kudryashova, V. A. Vibronic interaction in europium nitrates Eu(NO3)3·4SOR2. Spectrochim. Acta 2000, 56, 1149. https://doi.org/10.1016/s1386-1425(99)00213-9.Suche in Google Scholar
29. Steppert, M., Cisarova, I., Fanghänel, T., Geist, A., Lindqvist-Reis, P., Panak, P., Stepnicka, P., Trumm, S., Walther, C. Complexation of europium(III) by bis(dialkyltriazinyl)bipyridines in 1-octanol. Inorg. Chem. 2012, 51, 591. https://doi.org/10.1021/ic202119x.Suche in Google Scholar
30. Chodos, S. L., Satten, R. A. Model calculation of vibronic sidebands in Cs2UBr6. J. Chem. Phys. 1975, 62, 2411. https://doi.org/10.1063/1.430767.Suche in Google Scholar
31. Iben, I. E., Stavola, M., Macgregor, R. B., Zhang, X. Y., Friedman, J. M. Gd3+ vibronic side band spectroscopy. New optical probe of Ca2+ binding sites applied to biological macromolecules. Biophys. J. 1991, 59, 1040. https://doi.org/10.1016/s0006-3495(91)82319-0.Suche in Google Scholar
Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/ract-2021-1134).
© 2022 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Original Papers
- Spectroscopic investigation of the different complexation and extraction properties of diastereomeric diglycolamide ligands
- Influence of plutonium oxidation state on the formation of molecular hydrogen, nitrous acid and nitrous oxide from alpha radiolysis of nitric acid solution
- Efficient enrichment of U(VI) by two-dimensional layered transition metal carbide composite
- Application of artificial neural networks for predicting the isotopic composition of high burn-up solid plutonium sample using the 90–105 keV gamma-spectrum region
- Efficient and selective adsorption of U(VI) by succinic acid modified iron oxide adsorbent
- Electrochemical reduction of uranium and rhenium in hydrochloric acid system
- A sensitive improved method for analyzing diffusion coefficients of Cs in compacted bentonite with different lengths
- Adsorption behavior of chromium in an aqueous suspension of δ-alumina in absence and in presence of humic substances
- A novel theranostic probe [111In]In-DO3A-NHS-nimotuzumab in glioma xenograft
- Lead-free Sb-based polymer composite for γ-ray shielding purposes
Artikel in diesem Heft
- Frontmatter
- Original Papers
- Spectroscopic investigation of the different complexation and extraction properties of diastereomeric diglycolamide ligands
- Influence of plutonium oxidation state on the formation of molecular hydrogen, nitrous acid and nitrous oxide from alpha radiolysis of nitric acid solution
- Efficient enrichment of U(VI) by two-dimensional layered transition metal carbide composite
- Application of artificial neural networks for predicting the isotopic composition of high burn-up solid plutonium sample using the 90–105 keV gamma-spectrum region
- Efficient and selective adsorption of U(VI) by succinic acid modified iron oxide adsorbent
- Electrochemical reduction of uranium and rhenium in hydrochloric acid system
- A sensitive improved method for analyzing diffusion coefficients of Cs in compacted bentonite with different lengths
- Adsorption behavior of chromium in an aqueous suspension of δ-alumina in absence and in presence of humic substances
- A novel theranostic probe [111In]In-DO3A-NHS-nimotuzumab in glioma xenograft
- Lead-free Sb-based polymer composite for γ-ray shielding purposes
