Do Perchlorate and Triflate Anions Bind to the Uranyl Cation in an Acidic Aqueous Medium? A Combined EXAFS and Quantum Mechanical Investigation

Sémon, Laurent; Boehme, Christian; Billard, Isabelle; Hennig, Christoph; Lützenkirchen, K.; Reich, Tobias; Roßberg, André; Rossini, Isabelle; Wipff, Georges

doi:10.1002/1439-7641(20011015)2:10<591::aid-cphc591>3.3.co;2-2

Cited by 39 publications

(59 citation statements)

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“…On the basis of data [48]. In the case of HClO 4 , this is in line with the non-complexing ability of ClO À 4 towards U(VI) [49]. In the case of HNO 3 , in contrast, the aqueous speciation of uranium is well documented with evidence for the formation of two nitrato-complexes UO 2 NO 3 ð Þ þ and UO 2 (NO 3 ) 2 [50].…”

Section: Discussionsupporting

confidence: 58%

“…The data in HClO 4 medium appear to contrast with the HNO 3 case at first sight. Actually, neither the decrease in D U as a function of HClO 4 in the range 0-3.8 molÁL -1 nor the increase in D U above HClO 4 = 3.8 molÁL -1 can be ascribed to aqueous complexation because no perchlorate-U(VI) complexes are known in this range of acid concentration [49]. A qualitative explanation has thus to be found in another specific behavior of the perchloric acid system.…”

Section: Discussionmentioning

confidence: 93%

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New Ionic Liquid Based on the CMPO Pattern for the Sequential Extraction of U(VI), Am(III) and Eu(III)

et al. 2018

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Extraction of U(VI), Eu(III) and Am(III) has been performed from acidic aqueous solutions (HNO 3 , HClO 4) into the ionic liquid [C 4 mim][Tf 2 N] in which a new extracting taskspecific ionic liquid, based on the CMPO unit {namely 1-[3-[2-(octylphenylphosphoryl) acetamido]propyl]-3-methyl-1H-imidazol-3-ium bis(trifluoromethane)sulfonamide, hereafter noted OctPh-CMPO-IL}, was dissolved at low concentration (0.01 molÁL-1). EXAFS and UV-Vis spectroscopy measurements were performed to characterize the extracted species. The extraction of U(VI) is more efficient than the extraction of trivalent Am and Eu using this TSIL, for both acids and their concentration range. We obtained evidence that the metal ions are extracted as a solvate (UO 2 (OctPh-CMPO-IL) 3) by a cation exchange mechanism. Nitrate or perchlorate ions do not play a direct role in the extraction by being part of the extracted complexes, but the replacement of nitric acid for perchloric acid entails a drop in the selectivity between U and Eu. However, our TSIL allows a sequential separation of U(VI) and Eu/Am(III) using the same HNO 3 concentration and same nature of the organic phase, just by changing the ligand concentration.

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Section: Discussionsupporting

confidence: 58%

Section: Discussionmentioning

confidence: 93%

New Ionic Liquid Based on the CMPO Pattern for the Sequential Extraction of U(VI), Am(III) and Eu(III)

et al. 2018

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“…17,21,27 All these calculations have been performed with the Gaussian09 program. 61 The basic unit for the development of the different potentials is the pentahydrated uranyl(vi) ion, [UO 2 (H 2 O) 5 ] 2+ , since it has been proposed to be the most stable aquaion 6,39,62,63 even though an equilibrium with the tetrahydrate has also been suggested. 62 The reference structure is obtained by QM geometry optimization enforcing D 5h symmetry.…”

Section: A Hydrated Ion Model Potential For Uranylmentioning

confidence: 99%

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

Pérez-Conesa

Torrico

Martı́nez

et al. 2016

The Journal of Chemical Physics

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A new ab initio interaction potential based on the hydrated ion concept has been developed to obtain the structure, energetics, and dynamics of the hydration of uranyl in aqueous solution. It is the first force field that explicitly parameterizes the interaction of the uranyl hydrate with bulk water molecules to accurately define the second-shell behavior. The [UO(HO)] presents a first hydration shell U-O average distance of 2.46 Å and a second hydration shell peak at 4.61 Å corresponding to 22 molecules using a coordination number definition based on a multisite solute cavity. The second shell solvent molecules have longer mean residence times than those corresponding to the divalent monatomic cations. The axial regions are relatively de-populated, lacking direct hydrogen bonding to apical oxygens. Angle-solved radial distribution functions as well as the spatial distribution functions show a strong anisotropy in the ion hydration. The [UO(HO)] solvent structure may be regarded as a combination of a conventional second hydration shell in the equatorial and bridge regions, and a clathrate-like low density region in the axial region. Translational diffusion coefficient, hydration enthalpy, power spectra of the main vibrational modes, and the EXAFS spectrum simulated from molecular dynamics trajectories agree fairly well with the experiment.

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“…A FT splitting in the first coordination sphere of UF 3 + was reasonably attributed to different M‐F and M‐O bond lengths, which clearly suggested that F − existed in the first solvation shell of U(IV). Semon et al investigated the structure of uranyl ions by EXAFS in acidic aqueous solutions containing perchlorate and triflate ions. It was concluded that perchlorate ions, even in a high concentration of 11.5 M do not bind to UO 2 2+ , while inner‐sphere complexation of the triflate ions with UO 2 2+ occurred in 10 M CF 3 SO 3 H solution.…”

Section: Determination Of Actinide Speciation By Xafsmentioning

confidence: 99%

“…Recently, DFT investigations on uranyl(VI) complexes with F − , Cl − , CN − , NC − and O 2 2− in solution suggested that the stability of these species decreased in the order of O 2 2‐ > F − > Cl − > NC − > CN − . Combining EXAFS and QM studies, the interaction energies of some anions to uranyl cations were found to follow the order of perchlorate <triflate<nitrate . Additionally, BF 4 − and PF 6 − coordinated in monodentate fashion to uranyl forming inner‐sphere complexes, while the Tf 2 N − anion showed poor complexation ability to uranyl in aqueous solution .…”

Section: Actinide Computational Chemistry Associated With Exafs and Xmentioning

confidence: 99%

Exploring Actinide Materials Through Synchrotron Radiation Techniques

et al. 2014

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Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide‐based materials. This trend is partially driven by the basic needs for multi‐scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X‐ray absorption spectroscopy, X‐ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well.

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Do Perchlorate and Triflate Anions Bind to the Uranyl Cation in an Acidic Aqueous Medium? A Combined EXAFS and Quantum Mechanical Investigation

Cited by 39 publications

References 0 publications

New Ionic Liquid Based on the CMPO Pattern for the Sequential Extraction of U(VI), Am(III) and Eu(III)

New Ionic Liquid Based on the CMPO Pattern for the Sequential Extraction of U(VI), Am(III) and Eu(III)

A hydrated ion model of [UO2]2+ in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

Exploring Actinide Materials Through Synchrotron Radiation Techniques

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