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1. X-ray absorption spectroscopy and actinide electrochemistry: a setup dedicated to radioactive samples applied to neptunium chemistry

Author

Richard Husar, Thomas Dumas, Michel L. Schlegel, Daniel Schlegel, Dominique Guillaumont, Pier-Lorenzo Solari, and Philippe Moisy

Subjects
x-ray absorption spectroscopy, xas, actinide, electrochemistry, radioactive sample, neptunium chemistry, Nuclear and particle physics. Atomic energy. Radioactivity, QC770-798, Crystallography, QD901-999
Abstract

A spectroelectrochemical setup has been developed to investigate radioactive elements in small volumes (0.7 to 2 ml) under oxidation–reduction (redox) controlled conditions by X-ray absorption spectroscopy (XAS). The cell design is presented together with in situ XAS measurements performed during neptunium redox reactions. Cycling experiments on the NpO22+/NpO2+ redox couple were applied to qualify the cell electrodynamics using XANES measurements and its ability to probe modifications in the neptunyl hydration shell in a 1 mol l−1 HNO3 solution. The XAS results are in agreement with previous structural studies and the NpO22+/NpO2+ standard potential, determined using Nernst methods, is consistent with measurements based on other techniques. Subsequently, the NpO2+, NpO22+ and Np4+ ion structures in solution were stabilized and measured using EXAFS. The resulting fit parameters are again compared with other results from the literature and with theoretical models in order to evaluate how this spectroelectrochemistry experiment succeeds or fails to stabilize the oxidation states of actinides. The experiment succeeded in: (i) implementing a robust and safe XAS device to investigate unstable radioactive species, (ii) evaluate in a reproducible manner the NpO22+/NpO2+ standard potential under dilute conditions and (iii) clarify mechanistic aspects of the actinyl hydration sphere in solution. In contrast, a detailed comparison of EXAFS fit parameters shows that this method is less appropriate than the majority of the previously reported chemical methods for the stabilization of the Np4+ ion.

Published
2022
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2. Ultrasonically controlled synthesis of UO2+xcolloidal nanoparticles

Author

Manon Cot-Auriol, Matthieu Virot, Thomas Dumas, Olivier Diat, Xavier Le Goff, Philippe Moisy, and Sergey I. Nikitenko

Subjects
Inorganic Chemistry
Abstract

Sonochemistry was used for the preparation of uranium oxide nanoparticles. In comparison to classical hydrolysis approach, larger, better defined and more crystalline UO2+xnanoparticles were observed under ultrasound.

Published
2023
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3. Pourbaix Diagram of Astatine Revisited: Experimental Investigations

Author

Lu Liu, Rémi Maurice, Nicolas Galland, Philippe Moisy, Julie Champion, Gilles Montavon, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), the GIP ARRONAX for the production of At-211., and ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011)

Subjects
Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract

International audience; The Pourbaix diagram of an element displays its stable chemical forms with respect to the redox potential and pH of the solution, whose knowledge is fundamental for understanding and anticipating the chemistry of the element in a specified solution. Unlike most halogens, the Pourbaix diagram in the aqueous phase for astatine (At, Z = 85) is still under construction. In particular, the predominant domains of two astatine species assumed to exist under alkaline conditions, At$^-$ and AtO(OH)$_2$$^-$, need to be refined. Through high-performance ion-exchange chromatography, electromobility measurements, and competition experiments, the existence of At$^-$ and AtO(OH)$_2$$^-$ has been confirmed and the associated standard potential has been determined for the first time (0.86 ± 0.05 V vs the standard hydrogen electrode). On the basis of these results, a revised version of astatine’s Pourbaix diagram is proposed, covering the three oxidation states of astatine that exist in the thermodynamic stability range of water: At(-I), At(I), and At(III) (as $_2$$^-$, $_2$$^+$, AtO(+), AtO(OH), and AtO(OH)$_2$$^-$

Published
2022
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4. Investigation of the Plutonium(IV) Interactions with Two Variants of the EF-Hand Ca-Binding Site I of Calmodulin

Author

Loïc Daronnat, Vanessa Holfeltz, Nathalie Boubals, Thomas Dumas, Philippe Guilbaud, Diego Moreno Martinez, Philippe Moisy, Sandrine Sauge-Merle, David Lemaire, Pier Lorenzo Solari, Laurence Berthon, Catherine Berthomieu, Interactions Protéine Métal (IPM), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Inorganic Chemistry, [SDV]Life Sciences [q-bio], Physical and Theoretical Chemistry
Abstract

International audience; Due to its presence in the nuclear industry and its strong radiotoxicity, plutonium is an actinide of major interest in the event of internal contamination. To improve the understanding of its mechanisms of transport and accumulation in the body, the complexation of Pu(IV) to the most common protein calcium-binding motif found in cells, the EF-hand motif of calmodulin, was investigated. Visible and X-ray absorption spectroscopies (XAS) in solution made it possible to investigate the speciation of plutonium at physiological pH (pH 7.4) and pH 6 in two variants of the calmodulin Ca-binding site I and using Pu(IV) in different media: carbonate, chloride, or nitrate solutions. Three different species of Pu were identified in the samples, with formation of 1:1 Pu(IV):calmodulin peptide complexes, Pu(IV) reduction, and formation of peptide-mediated Pu(IV) hexanuclear cluster.

Published
2023
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5. Reactions of methyl, hydroxyl and peroxyl radicals with the DOTA chelating agent used in medical imaging

Author

Elad Avraham, Dan Meyerstein, Ana Lerner, Guy Yardeni, Svetlana Pevzner, Israel Zilbermann, Philippe Moisy, Eric Maimon, and Inna Popivker

Subjects
Diagnostic Imaging, Heterocyclic Compounds, 1-Ring, Free Radicals, Hydroxyl Radical, Physiology (medical), Biochemistry, Chelating Agents, Peroxides
Abstract

The mechanism of reaction of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) with ·CH

Published
2022
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6. First observation of [Pu6(OH)4O4 ]12+ cluster during the hydrolytic formation of PuO2 nanoparticles using H/D kinetic isotope effect

Author

Manon Cot-Auriol, Matthieu Virot, Thomas Dumas, Olivier Diat, Denis Menut, Philippe Moisy, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ions aux Interfaces Actives (L2IA), Synchrotron SOLEIL (SSOLEIL), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials Chemistry, Metals and Alloys, Ceramics and Composites, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

New insights are provided about the formation mechanism of PuO2 nanoparticles (NPs) by investigating an unprecedented kinetic isotope effect observed during their hydrolytic synthesis in H2O or D2O media.

Published
2022
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7. Synthesis and multi-scale properties of PuO2 nanoparticles: recent advances and open questions

Author

Matthieu Virot, Thomas Dumas, Manon Cot-Auriol, Philippe Moisy, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
General Engineering, General Materials Science, Bioengineering, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Atomic and Molecular Physics, and Optics
Abstract

The review focuses on the recent relevant progresses observed about PuO2 nanoparticle syntheses and characterizations including the recently deciphered electronic, structural and physico-chemical properties.

Published
2022
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10. A 70‐Year‐Old Mystery in Technetium Chemistry Explained by the New Technetium Polyoxometalate [H 7 O 3 ] 4 [Tc 20 O 68 ] ⋅ 4H 2 O

Author

Thomas Dumas, Mikhail S. Grigoriev, Frederic Poineau, Konstantin E. German, Paul M. Forster, Alexander M. Fedoseev, Christophe Den Auwer, Keith V. Lawler, G. A. Kirakosyan, and Philippe Moisy

Subjects
Aqueous solution, Absorption spectroscopy, Hydronium, Chemistry, Organic Chemistry, General Chemistry, Ring (chemistry), Catalysis, Molecular electronic transition, Crystallography, chemistry.chemical_compound, Octahedron, Polyoxometalate, Molecule
Abstract

[H7 O3 ]4 [Tc20 O68 ] ⋅ 4H2 O [1] was prepared from an aqueous Tc2 O7 solution concentrated over anhydrous H2 SO4 . [Tc20 O68 ]4- is the first polyanionic species to be reported for Tc. The unit cell contains one centrosymmetric [Tc20 O68 ]4- polyanion as well as hydronium ions and water molecules. The core of the structure consists of four Tc(V)O6 octahedra that form a square Tc4 O4 ring. The four Tc(V)O6 octahedra are decorated by sixteen Tc(VII)O4 tetrahedra. Calculations show the bonding within the Tc4 O4 ring to consist of a 3-center bond formed between each neighboring pair of Tc atoms and their bridging oxygen. Calculations also indicate that a strong d→d electronic transition at 513 nm is the origin of the red color of [1]. The characterization of red HTcO4 solutions by X-ray absorption spectroscopy has complemented the description of this compound in aqueous solution. The formation mechanisms in solution, including the possible role of technetium's radioactivity in the formation of [1], are discussed.

Published
2021
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11. Sonochemistry of actinides: from ions to nanoparticles and beyond

Author

Sergey I. Nikitenko, Matthieu Virot, Philippe Moisy, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[CHIM]Chemical Sciences, Physical and Theoretical Chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

Sonochemistry studies chemical and physical effects in liquids submitted to power ultrasound. These effects arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species. In principle, each cavitation bubble can be considered as a microreactor initiating chemical reactions at mild conditions. In addition, microjets and shock waves accompanied bubble collapse produce fragmentation, dispersion and erosion of solid surfaces or particles. Microbubbles oscillating in liquids also enable nucleation and precipitation of nanosized actinide compounds with specific morphology. This review focuses on the versatile sonochemical processes with actinide ions and particles in homogenous solutions and heterogenous systems. The redox reactions in aqueous solutions, dissolution or precipitation of refractory solids, synthesis of actinide nanoparticles, and ultrasonically driving decontamination are considered. The guideline for further research is also discussed.

Published
2022
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13. Redox Properties of CeIVDOTA in Carbonated Aqueous Solutions. A Radiolytic and an Electrochemical Study

Author

Inna Popivker, Eric Maimon, Svetlana Pevzner, Tomer Zidki, Dan Meyerstein, Israel Zilbermann, Philippe Moisy, Guy Yardeni, Haim Cohen, Dalia Gitin, and Elad Avraham

Subjects
Aqueous solution, 010304 chemical physics, Bicarbonate, Inorganic chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Redox, 0104 chemical sciences, Cerium, chemistry.chemical_compound, Electron transfer, Reaction rate constant, chemistry, 0103 physical sciences, Radiolysis, Carbonate, Physical and Theoretical Chemistry
Abstract

The redox chemistry of CeIIIDOTA in cage in carbonate solutions was studied using electrochemistry and radiolysis techniques (continuous radiolysis and pulse radiolysis). Spectroscopic measurements point out that the species present in the solutions at high bicarbonate concentrations are [CeIIIDOTA(CO3)]3- (or less plausible [CeIIIDOTA(HCO3)]2-) with the carbonate (bicarbonate) anion as the ninth ligand versus [CeIIIDOTA(H2O)]- present in the absence of bicarbonate. Electrochemical results show a relatively low increase in the thermodynamic stabilization of the redox couple CeIV/III in the presence of carbonate versus its aqueous analogue. [CeIVDOTA(CO3)]2- and [CeIVDOTA(H2O)], prepared electrochemically, decompose photolytically. However, kept in the dark, both are relatively long lived; [CeIVDOTA(H2O)], though, is orders of magnitude kinetically more stable (a considerably longer half-life). Thus, one concludes that the carbonate species have a different mechanism of decomposition depending also on the presence of dioxygen after its preparation (in deaerated/aerated solutions). The [CeIVDOTA(CO3)]2- species is produced radiolytically by oxidation of the trivalent species by CO3•- with a rate constant, measured using pulse radiolysis, of 3.3 × 105 M-1 s-1. This rate constant is at least 1 order of magnitude smaller than most of the rate constants so far reported for the reaction of CO3•- with transition metal/lanthanide (cerium)/actinide complexes. This result together with the bulkiness of the reactants might suggest an outer-sphere electron transfer rather than the inner-sphere one so far proposed. The lifetime of the tetravalent cerium species obtained radiolytically in the presence of carbonate is shorter than the electrochemical one, suggesting a different conformer involved.

Published
2021
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14. Modeling and Speciation Study of Uranium(VI) and Technetium(VII) with TBP

Author

P. Moeyaert, Alexiane Thevenet, Christian Sorel, Pier Lorenzo Solari, Thomas Dumas, Claire Lefebvre, Dominique Guillaumont, and Philippe Moisy

Subjects
Fission products, Extended X-ray absorption fine structure, General Chemical Engineering, digestive, oral, and skin physiology, Radiochemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, Rhenium, Uranium, 010403 inorganic & nuclear chemistry, Technetium, 01 natural sciences, XANES, Spent nuclear fuel, 0104 chemical sciences, 020401 chemical engineering, chemistry, Genetic algorithm, 0204 chemical engineering
Abstract

Among the fission products present in the spent nuclear fuel, technetium exhibits a singular behavior in reprocessing operations performed by solvent extraction. Indeed, this strong acid readily dissociates to form the oxo-anion TcO4− that may interfere with uranium(VI), plutonium(IV), and zirconium(IV) in the extraction cycles of the PUREX process. This paper focuses on the uranium-technetium complex with TBP and on its non-radioactive rhenium surrogate. Despite the large set of distribution data available for rhenium and technetium extraction with TBP, the structures of the co-extracted complexes remain largely unknown. However, it is important to understand clearly the extraction mechanism of technetium with TBP in the PUREX process to optimize the separation process and to model its behavior during the extraction steps. Based on distribution data available in the literature, a thermodynamic model was developed for the extraction of technetium with TBP for a large excess of uranium(VI) in organic phase. A good representation of uranium and technetium distribution data was thus obtained when considering the formation of (HTcO4)(TBP)n complexes, as well as mixed UO2(NO3)(TcO4)(HNO3)x(TBP)n, complexes. In the complex UO2(NO3)2(HNO3)x(TBP)n., one pertechnetate anion replaces one nitrate in the uranium coordination sphere. Combination of complementary spectroscopic techniques (FT-IR and X-ray absorption) supported by theoretical calculations (density functional theory) with organic phases containing a large excess of technetium(VII) or rhenium(VII) enabled full characterization of the limit mixed uranium−technetium species and also of mixed uranium-rhenium species. Details on the coordination of the uranium-technetium complex are provided with the help of DFT calculations and XAS measurements.

Published
2020
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15. On the Aqueous Chemistry of the UIV–DOTA Complex

Author

Ana Lerner, Radion Vainer, Yeshayahu Ben-Eliyahu, Claude Berthon, Yulia Moiseev, Marie-Claire Illy, Philippe Moisy, Israel Zilbermann, Gev Dovrat, Moshe H. Mintz, Eric Maimon, and Armand Bettelheim

Subjects
Aqueous solution, 010405 organic chemistry, Ligand, Organic Chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymer chemistry, Hydroxide, DOTA, Chelation, Fluoride
Abstract

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of UIV with H2 O, OH- , and F- as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The UIV -DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The UIV /UIII redox couple was found to be quasi-reversible for the complex with both axially bonded H2 O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron UV /UIV oxidation of the [UIV (DOTA)(H2 O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated UV cation.

Published
2020
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16. Role of the Hydroxo Group in the Coordination of Citric Acid to Trivalent Americium

Author

Christelle Tamain, Laura Bonato, Pier Lorenzo Solari, Atsushi Ikeda-Ohno, Astrid Barkleit, Dominique Guillaumont, Thomas Dumas, Jean Aupiais, Philippe Moisy, Philippe Guilbaud, Claude Berthon, Laboratory of Interactions Ligand-Actinide (LILA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Analyse, Géométrie et Modélisation (AGM - UMR 8088), Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY), Département RadioChimie et Procédés (DRCP), Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and CY Cergy Paris Université (CY)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Coordination sphere, 010405 organic chemistry, media_common.quotation_subject, Inorganic chemistry, chemistry.chemical_element, Americium, Actinide, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, chemistry.chemical_compound, Speciation, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Group (periodic table), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Citric acid, [CHIM.RADIO]Chemical Sciences/Radiochemistry, ComputingMilieux_MISCELLANEOUS, media_common
Abstract

International audience

Published
2020
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17. Characterization of a Hexanuclear Plutonium(IV) Nanostructure in an Acetate Solution via Visible-Near Infrared Absorption Spectroscopy, Extended X-ray Absorption Fine Structure Spectroscopy, and Density Functional Theory

Author

Geoffroy Chupin, Christelle Tamain, Thomas Dumas, Pier Lorenzo Solari, Philippe Moisy, and Dominique Guillaumont

Subjects
Inorganic Chemistry, Physical and Theoretical Chemistry
Abstract

A new hexanuclear plutonium cluster has been stabilized in aqueous media with acetate ligands. To probe the formation of such a complex structure, visible-near infrared (vis-NIR) absorption spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) were combined. The presence of Pu

Published
2022

18. Soft Hydrothermal Synthesis of Hafnon, HfSiO4

Author

Paul Estevenon, Adel Mesbah, Stéphanie Szenknect, Mohamed Ruwaid Rafiuddin, Nicolas Dacheux, Christophe Poinssot, Thibault Kaczmarek, Philippe Moisy, Eleonore Welcomme, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, General Chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Silicate, 0104 chemical sciences, wet chemistry route, hydrothermal synthesis, chemistry.chemical_compound, Hafnon, Chemical engineering, chemistry, [CHIM]Chemical Sciences, hafnium silicate, Hydrothermal synthesis, General Materials Science, zircon structure type, ComputingMilieux_MISCELLANEOUS, hafnon
Abstract

Despite being a member of the zircon type silicate family, the conditions allowing the hydrothermal synthesis of HfSiO4 were not well constrained. A multiparametric study was performed in order to follow the synthesis of this phase under soft hydro-thermal conditions and thus to determine the most efficient conditions to form single phase samples. Among the experi-mental parameters investigated, concentration of reactants, pH of the reactive media, temperature and duration of the hydrothermal treatment impacted significantly the formation rate of hafnon and its crystallization state. Pure HfSiO4 was obtained in acid reactive media with an acidity ranging from CHCl = 1.5 M to pH = 1.0 and for CSi ≈ CHf ≥ 0.21 mol·L 1. The silicate phase was prepared after a 24-hours treatment at temperatures ranging from 150°C to 250°C. However, rise of tem-perature and extension of the duration of the hydrothermal treatment favored the crystallization state of the final HfSiO4 samples.

Published
2020
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19. The Np V and Pu V Carbonate Systems: Thermodynamics and Coordination Chemistry

Author

Sylvain Topin, Jean-Charles Alexandre, Nicolas Dacheux, Rémi Sicre, Jean Aupiais, Bruno Siberchicot, and Philippe Moisy

Subjects
Inorganic Chemistry, chemistry.chemical_classification, chemistry.chemical_compound, Capillary electrophoresis, chemistry, Computational chemistry, Carbonate, Actinide, Quantum molecular dynamics, Coordination complex
Published
2020
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20. Crystallographic structure and crystal field parameters in the [AnIV(DPA)3]2− series, An = Th, U, Np, Pu

Author

Claude Berthon, Nicolas Galland, Christelle Tamain, Hélène Bolvin, Matthieu Autillo, Philippe Moisy, Julien Pilmé, Md. Ashraful Islam, Laetitia Guerin, and Julie Jung

Subjects
Electron density, Materials science, Field (physics), Series (mathematics), 010405 organic chemistry, Atoms in molecules, General Physics and Astronomy, Infrared spectroscopy, Crystal structure, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Crystal, Covalent bond, Physical chemistry, Physical and Theoretical Chemistry
Abstract

The [AnIV(DPA)3]2− series with An = Th, U, Np, Pu has been synthesized and characterized using SC-XRD and vibrational spectroscopy. First principles calculations were performed, the total electron density is analyzed using the Quantum Theory of Atoms in Molecules. Crystal field parameters and strength parameters are deduced following a previous work on the LnIII analog series e.g. [J. Jung et al., Chem. – Eur. J., 2019, 25, 15112]. The trends in the parameters along the series are compared to the LnIII complexes. They evidence larger covalent interactions and larger J mixing.

Published
2020
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21. Relevance of formation conditions to the size, morphology and local structure of intrinsic plutonium colloids

Author

Olivier Diat, Laurent Venault, Sandrine Dourdain, Thomas Dumas, Matthieu Virot, Philippe Moisy, Denis Menut, Cyril Micheau, Pier Lorenzo Solari, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Ions aux Interfaces Actives (L2IA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'Energie Atomique, Saclay (CEA)

Subjects
X-ray absorption spectroscopy, Materials science, Absorption spectroscopy, Small-angle X-ray scattering, Scattering, Materials Science (miscellaneous), Nanoparticle, Ionic bonding, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010501 environmental sciences, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid, Chemical physics, Particle size, [CHIM.RADIO]Chemical Sciences/Radiochemistry, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, General Environmental Science
Abstract

International audience; Fundamental knowledge about plutonium intrinsic colloids is a key issue for the prediction of plutonium transport and release rates in the environment. Recent studies demonstrated that the particle size and surface properties of intrinsic Pu colloids are strongly influenced by the preparation method. In this work, a combination of synchrotron small angle X-ray scattering (SAXS) with X-ray absorption spectroscopy (XAS) is used to characterize two kinds of stable plutonium intrinsic colloids prepared by hydrolysis of Pu(IV) ionic species and sonolysis of PuO2 in pure water. Despite their similarities, the multi-scale structural properties of these colloidal suspensions are found to be strongly influenced by the synthesis route. The hydrolysis approach leads to spherical nanoparticles of ca. 2.0 nm, whereas sonolytic colloids show elongated structures measuring 5.7 nm of thickness and >30 nm long. This difference results from the synthesis mechanism and can be attributed to nanoparticle aggregation in the absence of capping-ions. The results obtained by both SAXS and XAS approaches converge in the description of Pu(IV) intrinsic colloids as core–shell nanoparticles made up of a PuO2 core covered with a disordered Pu–O shell characterized by a splitting of Pu–O and Pu–Pu distances and an associated strong increase of associated DWF parameters. The local distortions of both Pu–O and Pu–Pu coordination spheres observed by XAS seem to be correlated with the nanoparticle shrinking probed by SAXS rather from the contribution of higher Pu oxidation states. The stabilization of the hydrolytic colloidal particles is further suggested from SAXS simulation to result from interaction with counter-ions from the medium.

Published
2020
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22. Ultrasonically assisted conversion of uranium trioxide into uranium( vi ) intrinsic colloids

Author

Christophe Den Auwer, Xavier Le Goff, Olivier Diat, Thomas Dumas, Cyril Micheau, Manon Cot-Auriol, Philippe Moisy, Matthieu Virot, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Ions aux Interfaces Actives (L2IA), Commission des méthodes d'analyse du CEA (CETAMA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Nice Sophia Antipolis (1965 - 2019) (UNS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Inorganic chemistry, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, Uranium, 010402 general chemistry, 021001 nanoscience & nanotechnology, Uranyl, complex mixtures, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, 13. Climate action, Uranium trioxide, Oxidizing agent, [CHIM]Chemical Sciences, Reactivity (chemistry), Leaching (metallurgy), 0210 nano-technology, Schoepite
Abstract

Under oxidizing conditions, the corrosion of spent nuclear fuel may lead to the leaching of radionuclides including soluble uranyl-based species. The speciation of the generated chemical forms is complex and the related potential formation of colloidal species appears surprisingly poorly reported in the literature. Their formation could however contribute significantly to the mobility of radionuclides in the environment. A better knowledge in the speciation and reactivity of these species appears particularly relevant. This study describes the preparation and characterization of intrinsic uranium(VI) colloids from amorphous and crystalline UO3 in pure water assisted by 20 kHz ultrasound. In the presence of carbon monoxide preventing the sonochemical formation of hydrogen peroxide, ultrasonic treatment boosts the conversion of UO3 powder into (meta-)schoepite precipitates and yields very stable and notably concentrated uranium(VI) nanoparticles in the liquid phase. Using HR-TEM, SAXS and XAS techniques, we confirmed that the colloidal suspension is composed of quasi-spherical nanoparticles measuring ca. 3.8 ± 0.3 nm and exhibiting a schoepite-like crystallographic structure. The proposed method demonstrates the possible formation of environmentally relevant U(VI) colloidal nanoparticles appearing particularly interesting for the preparation of reference systems in the absence of added ions and capping agents.

Published
2021
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23. Electrochemical Behavior of Ce(IV)/Ce(III) Couple in N,N‐Di(2‐ethylhexyl)‐n‐butanamide (DEHBA), N,N‐Di(2‐ethylhexyl)‐iso‐butanamide (DEHiBA), and N,N‐Di(2‐ethylhexyl)‐3,3‐dimethyl Butanamide (DEHDMBA)

Author

Fethi Bedioui, Philippe Moisy, Amivi Felicite Amoudji, Sylvie Arpigny, Commission des méthodes d'analyse du CEA (CETAMA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)

Subjects
dialkylamide, chemistry.chemical_element, PUREX, 010402 general chemistry, 010403 inorganic & nuclear chemistry, Electrochemistry, 01 natural sciences, cyclic voltammetry, 0104 chemical sciences, Analytical Chemistry, Cerium, cerium, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Cyclic voltammetry, Nuclear chemistry
Abstract

International audience; In this work we report on the electrochemical behavior of Ce(IV)/Ce(III) redox couple in pure N,N-dialkyl amides (N,N-DA), namely N,N-di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,Ndi(2-ethylhexyl)-3,3-dimethyl butanamide (DEHDMBA) equilibrated with nitric aqueous solutions as an entry to the direct electrochemical characterization of plutonium in these extractants. Ce(IV)/Ce(III) redox process was used as a model. Its potential (E 1/2  1.02 V/SCE) is not affected by the temperature and the nature of the N,N-DA and this clearly indicates that the functionalities of the these extractants produce the same relative effect on both +IV and +III oxidation states of the cerium cation. Linear variations of the current intensity of the reduction peak of Ce(IV) with the concentration of Ce(IV)/N,N-DAs/HNO 3 (5M) solutions were obtained from cyclic voltammograms recorded at 25°C and 40°C. Due to the poor definition of the voltammograms in DEHiBA and DEHDMBA, such characterization allows only the evaluation of the performances of the chemical extraction of Ce(IV) from aqueous nitric acid solution by the undiluted DEHBA. To our knowledge, the electrochemical behavior of Ce(IV)/Ce(III) in N,N-DAs was not previously studied and our findings will for sure open the door for further investigations in this field.

Published
2021
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24. Monitoring and Management of Anions in Polluted Aqua Systems: case studies on nitrate, chromate, pertechnetate and diclofenac

Author

Peter Hesemann, Philippe Moisy, Amitabh Banerji, Rana Ahmed, Andreas Taubert, Universität Potsdam, Commissariat à l'Energie Atomique, Centre de Marcoule (CEA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), N.a. Oladoja, E.I. Unuabonah, University of Potsdam = Universität Potsdam, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Pertechnetate, Environmental remediation, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, chemistry.chemical_compound, Diclofenac, Nitrate, Nuclear industry, medicine, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Pollutant, Chromate conversion coating, biology, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 6. Clean water, chemistry, 13. Climate action, Environmental chemistry, [SDE]Environmental Sciences, biology.protein, Environmental science, 0210 nano-technology, Organic anion, medicine.drug
Abstract

Anionic pollutants are widespread and pose severe environmental risks. This chapter focuses on four different anions as representative examples for various classes of anionic pollutants originating from various anthropogenic sources and activities: nitrate from agriculture, chromate from leather and tanning industries, pertechnetate from nuclear industry and military activities and finally, as an example of an organic anion, diclofenac from the pharmaceutical industry. All four anions pose different risks, but their management calls for similar remediation strategies. This chapter summarizes these strategies and discusses their challenges, their advantages and disadvantages.

Published
2021

26. Real-Time Observation of Solvation Dynamics of Electron in Actinide Extraction Binary Solutions of Water and n-Tributyl Phosphate

Author

Jun Ma, Teseer Bahry, Mehran Mostafavi, Sergey A. Denisov, Philippe Moisy, Institut de Chimie Physique (ICP), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Commission des méthodes d'analyse du CEA (CETAMA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Nanjing University of Aeronautics and Astronautics [Nanjing] (NUAA)

Subjects
010304 chemical physics, Absorption spectroscopy, Chemistry, Solvation, Electron, 010402 general chemistry, Mole fraction, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Chemical physics, 0103 physical sciences, Materials Chemistry, Water environment, Molecule, Tributyl phosphate, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The excess electron in solution is a highly reactive radical involved in various radiation-induced reactions. Its solvation state critically determines the subsequent pathway and rate of transfer. For instance, water plays a dominating role in the electron-induced dealkylation of n-tributyl phosphate in actinide extraction processing. However, the underlying electron solvation processes in such systems are lacking. Herein, we directly observed the solvation dynamics of electrons in H-bonded water and n-tributyl phosphate (TBP) binary solutions with a mole fraction of water (Xw) varying from 0.05 to 0.51 under ambient conditions. Following the evolution of the absorption spectrum of trapped electrons (not fully solvated) with picosecond resolution, we show that electrons statistically distributed would undergo preferential solvation within water molecules extracted in TBP. We determine the time scale of excess electron full solvation from the deconvoluted transient absorption-kinetical data. The process of solvent reorganization accelerates by increasing the water molar fraction, and the rate of this process is 2 orders of magnitude slower compared to bulk water. We assigned the solvation process to hydrogen network reorientation induced by a negative charge of the excess electron that strongly depends on the local water environment. Our findings suggest that water significantly stabilizes the electron in a deeper potential than the pure TBP case. In its new state, the electron is likely to inhibit the dealkylation of extractants in actinide separation.

Published
2021
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27. Les actinides leur interaction avec les processus biologiques: où en sommes-nous?

Author

Claude Alban, Jean Aupiais, Maria Rosa Beccia, Catherine Berthomieu, Damien Bourgeois, Jacques Bourguignon, Carole Bresson, Carles, Georges F., Virginie Chapon, Gaelle Creff, Pascale Delangle, Christophe Den Auwer, Christophe Di Giorgio, Thomas Dumas, Philippe Guilbaud, Agnes Hagege, Veronique Malard, Philippe Moisy, Eduardo Paredes, Valérie Pierrefite-Carle, Stephane Ravanel, Sabine Santucci-Darmanin, Sandrine Sauge-Merle, Bruno Siberchicot, Pier Lorenzo Solari, Anne van der Meeren, Claude Vidaud, Plantes, Stress & Métaux (MetalStress), Physiologie cellulaire et végétale (LPCV), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Chimie de Nice (ICN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), Interactions Protéine Métal (IPM), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Systèmes HYbrides pour la Séparation (LHyS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, UMR E4320 (TIRO-MATOs), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Côte d'Azur (UCA), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Radiotoxicologie (LRT), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA Marcoule, Bagnols-sur-Ceze, France, Programme de Toxicologie nucléaire du CEA, Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and Martin-Laffon, Jacqueline

Subjects
[SDV.TOX] Life Sciences [q-bio]/Toxicology, [SDV.TOX]Life Sciences [q-bio]/Toxicology, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

28. Temperature Dependence of

Author

Matthieu, Autillo, Md Ashraful, Islam, Julie, Héron, Laetitia, Guérin, Eleonor, Acher, Christelle, Tamain, Marie-Claire, Illy, Philippe, Moisy, Eric, Colineau, Jean-Christophe, Griveau, Claude, Berthon, and Hélène, Bolvin

Abstract

Actinide +VI complexes (

Published
2020

29. Oligomers Intermediates in Between Two New Distinct Homonuclear Uranium(IV) DOTP Complexes*

Author

Eric Maimon, Mark Karpasas, Radion Vainer, Gev Dovrat, Israel Zilbermann, Svetlana Pevzner, Ana Lerner, Claude Berthon, Yeshayahu Ben-Elyiahu, Philippe Moisy, and Armand Bettelheim

Subjects
chemistry.chemical_classification, Aqueous solution, 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Homonuclear molecule, 0104 chemical sciences, Coordination complex, chemistry.chemical_compound, Crystallography, Macrocyclic ligand, Methylene, Absorption (chemistry), Stoichiometry
Abstract

Two new aqueous UIV complexes were synthesized by the interaction between the tetravalent uranium cation and the (1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid) (DOTP) macrocyclic ligand. Two distinct homonuclear complexes were identified; the first was characterized by X-ray crystallography as a unique "out-of-cage", [U(DOTPH6 )2 ] complex, in which the UIV cation is octa-coordinated to 4 phosphonic arms from each ligand in a square anti-prism geometry, with a C4 symmetry. The second is the "in-cage" [U(DOTPH4 )] complex, in which the tetravalent cation is located between the macrocycle O4 and N4 planes. With the help of UV-Vis absorption, 1 H/31 P NMR, ATR-IR, and MALDI-TOFMS analytical techniques, the chemical interchange between both species is presented. It is shown that the one-way transition is governed by the formation of a multiple number of soluble oligomeric species consisting of varied stoichiometric ratios of both characterized homonuclear complexes.

Published
2020

30. Sonochemical dissolution of nanoscale ThO2 and partial conversion into a thorium peroxo sulfate

Author

Laura Bonato, Matthieu Virot, Xavier Le Goff, Philippe Moisy, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Etude de la Matière en Mode Environnemental (L2ME), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Acoustics and Ultrasonics, Organic Chemistry, Inorganic chemistry, Thorium, chemistry.chemical_element, Sulfuric acid, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Cavitation, Chemical Engineering (miscellaneous), Environmental Chemistry, [CHIM]Chemical Sciences, Radiology, Nuclear Medicine and imaging, Sulfate, 0210 nano-technology, Dissolution, Nanoscopic scale
Abstract

International audience; The influence of the sample morphology and experimental conditions towards the sonochemical dissolution of nanoscale ThO 2 samples in sulfuric acid media is described. Significant sonochemical dissolution rates and yields are observed at 20 kHz under Ar/O 2 atmosphere in dilute 0.5 M H 2 SO 4 at room temperature, contrasting with the generally-reported high refractory behavior for ThO 2. The dissolution of ThO 2 combines the physical effects driven by acoustic cavitation phenomenon, the complexing affinity of Th(IV) in sulfuric medium and the sonochemical generation of H 2 O 2. These sonochemical conditions further allow the observation of the partial conversion of ThO 2 into a scarce Th(IV) peroxo sulfate with 1D morphology resulting from one or both following processes: dissolution/ reprecipitation or formation of an intermediate Th(IV) surface complex.

Published
2020
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31. In situ study of the synthesis of thorite (ThSiO 4 ) under environmental representative conditions

Author

Jérémy Causse, Nicolas Dacheux, Adel Mesbah, Eleonore Welcomme, Paul Estevenon, Philippe Moisy, Christophe Poinssot, Stéphanie Szenknect, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Thorium, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, Actinide, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Nanocrystalline material, Silicate, 0104 chemical sciences, Thorite, Inorganic Chemistry, chemistry.chemical_compound, Actinides in the environment, chemistry, Chemical engineering, 13. Climate action, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Zircon
Abstract

Thorite, (ThSiO4) with a zircon type structure, is one of the most abundant natural sources of thorium on Earth. Generally, actinides are known to form nanoparticles in silicate medium, though no direct link between those colloids and the crystalline form of thorite was evidenced until now. Here we show the formation of thorite from colloids and nanocrystalline structures under experimental conditions close to environmental pH and temperature. Through in situ small and wide angle X-ray scattering (SWAXS) measurements, colloids with a few nanometers in size were first evidenced at a low reaction time. These colloids have elongated shapes and finally tend to aggregate after their size has reached 10 nm. Once aggregated, the system goes through a maturation step, ending with the emergence of nanocrystallites as thorite zircon structures. This maturation step is longer when the reaction temperature is decreased which highlights the kinetic considerations. These results have potential implications on the paragenesis of Th mineral deposits and also in the behaviour of Th and, by analogy, tetravalent actinides in the environment. The significant characteristics of this work are that Th-silicate colloids were demonstrated at low temperatures and a near neutral pH with long-term stability and a morphology in favor of high mobility in groundwater. If these species are formed in more diluted media, this could be problematic owing to the spreading of Th and, by analogy, other tetravalent actinides in the environment.

Published
2020
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32. Crystallographic structure and crystal field parameters in the [An

Author

Matthieu, Autillo, Md Ashraful, Islam, Julie, Jung, Julien, Pilmé, Nicolas, Galland, Laetitia, Guerin, Philippe, Moisy, Claude, Berthon, Christelle, Tamain, and Hélène, Bolvin

Abstract

The [AnIV(DPA)3]2- series with An = Th, U, Np, Pu has been synthesized and characterized using SC-XRD and vibrational spectroscopy. First principles calculations were performed, the total electron density is analyzed using the Quantum Theory of Atoms in Molecules. Crystal field parameters and strength parameters are deduced following a previous work on the LnIII analog series e.g. [J. Jung et al., Chem. - Eur. J., 2019, 25, 15112]. The trends in the parameters along the series are compared to the LnIII complexes. They evidence larger covalent interactions and larger J mixing.

Published
2020

33. The formation of PuSiO4 under hydrothermal conditions

Author

Paul Estevenon, Gauthier Jouan, Nicolas Dacheux, Philippe Moisy, Christelle Tamain, Stéphanie Szenknect, Christophe Poinssot, Eleonore Welcomme, Adel Mesbah, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic chemistry, chemistry.chemical_element, Thorium, Hydrochloric acid, 02 engineering and technology, Uranium, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Silicate, Hydrothermal circulation, 0104 chemical sciences, Plutonium, Inorganic Chemistry, chemistry.chemical_compound, Cerium, chemistry, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract

Attempts to synthesize plutonium(iv) silicate, PuSiO4, have been made on the basis of results recently reported in the literature for CeSiO4, ThSiO4, and USiO4 under hydrothermal conditions. Although it was not possible to prepare PuSiO4via applying the conditions reported for thorium and uranium, an efficient method of PuSiO4 synthesis was established by applying the conditions optimized for the CeSiO4 system. This method was based on the slow oxidation of plutonium(iii) silicate reactants under hydrothermal conditions at 150 °C in hydrochloric acid (pH = 3-4). These results shed new light on the potential behavior of plutonium in reductive environments, highlighting the representative nature of cerium surrogates when studying plutonium under such conditions and providing some important pieces of information regarding plutonium chemistry in silicate solutions.

Published
2020
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34. Preparation of CeSiO4 from aqueous precursors under soft hydrothermal conditions

Author

Philippe Moisy, Adel Mesbah, Paul Estevenon, Eleonore Welcomme, Nicolas Dacheux, Christophe Poinssot, Stéphanie Szenknect, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aqueous solution, 010405 organic chemistry, Metal ions in aqueous solution, Inorganic chemistry, Hydrothermal treatment, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 6. Clean water, Silicate, Hydrothermal circulation, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Nitrate, Phase (matter), Single phase
Abstract

International audience; Even though CeSiO4 was synthesized one time through a hydrothermal treatment, the conditions leading to its formation remain largely unknown. In order to define the optimized conditions of synthesis, a multiparametric study was developed by varying the pH of the solution, the temperature, and the nature of the reactants and of the complexing ions in solution. This study highlighted that CeSiO4 could not be obtained starting from Ce(IV) reactants. An optimal set of conditions was defined to prepare single phase samples. Pure CeSiO4 was obtained through a hydrothermal treatment at 150 °C using a starting mixture of 1 mol L−1 Ce(III) nitrate and Na2SiO3 solutions and by adjusting the initial pH to 8. The chemical limitations observed during the synthesis of CeSiO4 suggested that the formation of this phase may result from the slow in situ oxidation of a Ce(III) silicate complex during the hydrothermal treatment.

Published
2019
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35. Thermodynamics of plutonium(<scp>iii</scp>) and curium(<scp>iii</scp>) complexation with a N-donor ligand

Author

Philippe Moisy, Denis Guillaneux, Dominique Guillaumont, Manuel Miguirditchian, Audrey Saint-Maxent, and Charles Madic

Subjects
Inorganic Chemistry, Isothermal microcalorimetry, chemistry, Curium, Ligand, Physical chemistry, chemistry.chemical_element, Plutonium
Abstract

The complexation of Pu(iii) and Cm(iii) with a soft N-donor ligand was investigated using the van't Hoff method, microcalorimetry and DFT calculations. The studies revealed that the strength of the actinide-ligand bond as given by the enthalpic contribution drastically decreases on going from Pu(iii) to Cm(iii), while the complex stability remains nearly constant.

Published
2019
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36. Electrochemical and Spectroscopic Study of Eu

Author

David, Bengio, Thomas, Dumas, Sylvie, Arpigny, Richard, Husar, Eric, Mendes, Pier Lorenzo, Solari, Michel L, Schlegel, Daniel, Schlegel, Stéphane, Pellet-Rostaing, and Philippe, Moisy

Abstract

Separation processes based on room temperature ionic liquids (RTIL) and electrochemical refining are promising strategies for the recovery of lanthanides from primary ores and electronic waste. However, they require the speciation of dissolved elements to be known with accuracy. In the present study, Eu coordination and Eu

Published
2020

37. Sonochemical dissolution of nanoscale ThO

Author

Laura, Bonato, Matthieu, Virot, Xavier, Le Goff, Philippe, Moisy, and Sergey I, Nikitenko

Abstract

The influence of the sample morphology and experimental conditions towards the sonochemical dissolution of nanoscale ThO

Published
2020

38. Guanidinium dioxidobis(picolinato-κ2N,O)(picolinato-κO)uranate(VI)

Author

Vitalii I. Mishkevich, Mikhail S. Grigoriev, Alexandre M. Fedosseev, and Philippe Moisy

Subjects
Crystallography, QD901-999
Abstract

In the title compound, (CH6N3)[U(C6H4NO2)3O2], the uranyl group is coordinated by two O and two N atoms from two chelating picolinate ligands, and one O atom from a third picolinate ligand. The coordination environment of the UVI atom (N2O5) is distorted pentagonal–bipyramidal. In the crystal, all amino groups are involved in the formation of N—H...O and N—H...N hydrogen bonds, which link cations and anions into layers parallel to the ac plane.

Published
2012
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39. Experimental Speciation of Plutonium(IV) in Natural Seawater

Author

Christophe Moulin, Jose Mustre de Leon, Christophe Den Auwer, Roberto A. Colina-Ruiz, Pier Lorenzo Solari, Philippe Moisy, Marguerite Monfort, Maria Rosa Beccia, Thomas Dumas, Mireille Guigue, and Minja Matara-aho

Subjects
Hydrogen compounds, 010405 organic chemistry, chemistry.chemical_element, General Chemistry, Actinide, 010402 general chemistry, 01 natural sciences, Natural (archaeology), 0104 chemical sciences, Plutonium, chemistry, Environmental chemistry, Genetic algorithm, Seawater, Transuranium element
Published
2018
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40. Dissolution of Th0.25U0.75O2 sintered pellets: Impact of nitrate ions and nitrous acid

Author

Stéphanie Szenknect, Philippe Moisy, Laurent Claparede, Thomas Dalger, and Nicolas Dacheux

Subjects
Nitrous acid, Induction period, Inorganic chemistry, Kinetics, Metals and Alloys, chemistry.chemical_element, Nitrogen, Industrial and Manufacturing Engineering, chemistry.chemical_compound, chemistry, Nitrate, Nitric acid, Oxidizing agent, Materials Chemistry, Dissolution
Abstract

In order to gain insights on the kinetics of the dissolution of Gen(IV) MOX fuels, sintered pellets of Th0.25U0.75O2 were prepared as surrogates. Particularly, the impact of nitrogen species on the kinetics of dissolution of Th1-xUxO2 in nitric acid must be evaluated. In this work, various experiments were performed to determine the influence of nitrate ions and nitrous acid on the dissolution rate and mechanism of Th0.25U0.75O2 in nitric acid. It appeared that the addition of 3 mol L−1 NH4NO3 to the 1 mol L−1 HNO3 solution led to a strong increase of the dissolution rate. Thus, it seemed that the greatest impact on the dissolution kinetics during the induction period was associated to undissociated HNO3 instead of free nitrate ions. What is more, addition of a constant HNO2 concentration of 2 × 10−3 mol L−1 to 1 mol L−1 HNO3 induced a strong increase of the dissolution rate. However, the dissolution kinetics remained much faster in 4 mol L−1 HNO3, which was associated to the presence of an equivalent concentration of HNO2 in the solution. It then appeared that HNO2 species was not the prevailing species responsible for the catalysis of the dissolution kinetics of Th0.25U0.75O2. However, microstructural evolutions of the pellets dissolved in the presence of HNO2 showed the existence of small intra-granular corrosion pits covering the entire surface of the grains. That confirmed the highly oxidizing nature of HNO2 regarding to tetravalent uranium. Nevertheless, the presence of large cavities also suggested the existence of heterogeneous progress of the dissolution, associated to the existence of preferential dissolution zones consequently to the accumulation of reactive species in confined areas. Such reactive species might be HNO2, but more probably another unknown catalyst present at equilibrium with HNO2.

Published
2021
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41. Direct conversion of uranium dioxide UO

Author

Florian, Joly, Pardis, Simon, Xavier, Trivelli, Mehdi, Arab, Bertrand, Morel, Pier Lorenzo, Solari, Jean-Francois, Paul, Philippe, Moisy, and Christophe, Volkringer

Abstract

The industrial fluorination of UO2 to UF4 is based on a complex process involving the manipulation of a large amount of HF, a very toxic and corrosive gas. We present here a safer way to accomplish this reaction utilizing ionic liquid [Bmim][PF6] as a unique reaction medium and fluoride source.

Published
2019

42. On the Aqueous Chemistry of the U

Author

Gev, Dovrat, Marie-Claire, Illy, Claude, Berthon, Ana, Lerner, Moshe H, Mintz, Eric, Maimon, Radion, Vainer, Yeshayahu, Ben-Eliyahu, Yulia, Moiseev, Philippe, Moisy, Armand, Bettelheim, and Israel, Zilbermann

Abstract

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of U

Published
2019

43. Probing the local structure of nanoscale actinide oxides: a comparison between PuO

Author

Laura, Bonato, Matthieu, Virot, Thomas, Dumas, Adel, Mesbah, Elodie, Dalodière, Oliver, Dieste Blanco, Thierry, Wiss, Xavier, Le Goff, Michael, Odorico, Damien, Prieur, André, Rossberg, Laurent, Venault, Nicolas, Dacheux, Philippe, Moisy, and Sergey I, Nikitenko

Abstract

Actinide research at the nanoscale is gaining fundamental interest due to environmental and industrial issues. The knowledge of the local structure and speciation of actinide nanoparticles, which possibly exhibit specific physico-chemical properties in comparison to bulk materials, would help in a better and reliable description of their behaviour and reactivity. Herein, the synthesis and relevant characterization of PuO

Published
2019

44. Dihydrogen H$_2$ steady state in $\alpha$-radiolysis of water adsorbed on PuO$_2$ surface

Author

Jackie Vermeulen, Philippe Moisy, Nicolas Vigier, Jérémy Gaillard, Natalia Budanova, Laurent Venault, Arnaud Deroche, Olivier Lemaire, Jérôme Maurin, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ORANO, the Orano Group, CEA- Saclay (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Radiation, Hydrogen, 010308 nuclear & particles physics, Kinetics, chemistry.chemical_element, Thermal treatment, 01 natural sciences, 030218 nuclear medicine & medical imaging, 03 medical and health sciences, 0302 clinical medicine, Adsorption, chemistry, 13. Climate action, Chemical physics, Specific surface area, 0103 physical sciences, Radiolysis, [CHIM]Chemical Sciences, Relative humidity, Hydrogen production
Abstract

International audience; Radiolysis of water adsorbed on PuO$_2$ surface has been the subject of several studies but still remains poorly understood. The present study brings new experimental results helping to further understand the phenomena occurring at PuO$_2$ surface. Radiolysis of adsorbed water on PuO2 surface leads to the reach of a steady state in hydrogen content when relative humidity is kept constant implying an equilibrium between generation and consumption of hydrogen. The influences of specific surface area, relative humidity, PuO$_2$ dose rate and composition of the atmosphere (Ar vs air) on hydrogen generation were investigated. A significant evolution of the hydrogen generation kinetics was observed upon PuO$_2$ surface aging. This result might be related to an evolution of the surface physicochemical state induced by a long-term storage in H$_2$O/H$_2$/O$_2$ atmosphere. The surface evolution modifies the equilibrium between generation and consumption of hydrogen. Several annealing thermal treatment were necessary to retrieve H$_2$ accumulations kinetics similar to the ones obtained with the same sample as freshly prepared. This indicates an important evolution of PuO$_2$ surface and subsurface. A mechanism is described to explain the surface evolution and its effect on H$_2$ accumulation through radiolysis of adsorbed water.

Published
2019
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45. Protactinium(V) in aqueous solution: a light actinide without actinyl moiety

Author

Christophe Den Auwer, Claire Le Naour, Philippe Moisy, Jean Aupiais, Jérôme Roques, Institut de Physique Nucléaire d'Orsay (IPNO), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Paris-Sud - Paris 11 (UP11), and Université Nice Sophia Antipolis (... - 2019) (UNS)

Subjects
Aqueous solution, 010405 organic chemistry, Inorganic chemistry, Protactinium, chemistry.chemical_element, Actinide, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry, Moiety, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

This review highlights recent data on the complexation of Pa(V) with inorganic (fluoride and sulphate) and organic (oxalate, nitrilotriacetate, diethylenetriaminepentaacetate) ligands in solution. New thermodynamic parameters relative to the complexation of Pa(V) with sulphate are presented. The review also includes gas phase and theoretical studies focused on the interaction of Pa(V) in the dioxo and oxo forms with water.

Published
2019
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46. Frontispiece: Deciphering the Crystal Structure of a Scarce 1D Polymeric Thorium Peroxo Sulfate

Author

Xavier F. Le Goff, Pierre Lecante, Thomas Dumas, Christoph Hennig, Adel Mesbah, Laura Bonato, Sergey I. Nikitenko, Damien Prieur, Nicolas Dacheux, Matthieu Virot, and Philippe Moisy

Subjects
010405 organic chemistry, Organic Chemistry, Inorganic chemistry, Thorium, chemistry.chemical_element, General Chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, Peroxide, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Sulfate
Published
2019
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47. Formation of CeSiO 4 from cerium( iii ) silicate precursors

Author

Thibault Kaczmarek, Philippe Moisy, Eleonore Welcomme, Thomas Dumas, Adel Mesbah, Stéphanie Szenknect, Nicolas Dacheux, Paul Estevenon, Pier Lorenzo Solari, Christophe Poinssot, Fabien Vadot, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
In situ, Aqueous solution, 010405 organic chemistry, chemistry.chemical_element, Hydrothermal treatment, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Silicate, Hydrothermal circulation, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Cerium, chemistry, Hydrothermal synthesis, [CHIM]Chemical Sciences, [CHIM.RADIO]Chemical Sciences/Radiochemistry, ComputingMilieux_MISCELLANEOUS, Oxidation rate, Nuclear chemistry
Abstract

Although the preparation of CeSiO4 has been already reported, the formation of pure cerium silicate from aqueous precursors appears as a challenge. An innovative way of synthesis has been identified in this study, allowing the formation of CeSiO4 after hydrothermal treatment starting from Ce(iii) silicate precursors. Among the experimental parameters examined, significant effects were found according to the nature of the precursor and of the reactive media considered, the pH of the reactive media and the temperature of the hydrothermal process. This study allows the determination of optimized conditions for the hydrothermal synthesis of pure CeSiO4 (A-Ce2Si2O7 or Ce4.67(SiO4)3O as starting precursors, nitric medium, pH = 7, 7 days at 150 °C). The in situ low oxidation rate of Ce(iii) into Ce(iv) was a key parameter to consider in order to avoid the presence of CeO2 in the final mixtures.

Published
2019
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48. Formation of CeSiO

Author

Paul, Estevenon, Thibault, Kaczmarek, Fabien, Vadot, Thomas, Dumas, Pier Lorenzo, Solari, Eleonore, Welcomme, Stephanie, Szenknect, Adel, Mesbah, Philippe, Moisy, Christophe, Poinssot, and Nicolas, Dacheux

Abstract

Although the preparation of CeSiO4 has been already reported, the formation of pure cerium silicate from aqueous precursors appears as a challenge. An innovative way of synthesis has been identified in this study, allowing the formation of CeSiO4 after hydrothermal treatment starting from Ce(iii) silicate precursors. Among the experimental parameters examined, significant effects were found according to the nature of the precursor and of the reactive media considered, the pH of the reactive media and the temperature of the hydrothermal process. This study allows the determination of optimized conditions for the hydrothermal synthesis of pure CeSiO4 (A-Ce2Si2O7 or Ce4.67(SiO4)3O as starting precursors, nitric medium, pH = 7, 7 days at 150 °C). The in situ low oxidation rate of Ce(iii) into Ce(iv) was a key parameter to consider in order to avoid the presence of CeO2 in the final mixtures.

Published
2019

49. Deciphering the Crystal Structure of a Scarce 1D Polymeric Thorium Peroxo Sulfate

Author

Laura Bonato, Pierre Lecante, Sergey I. Nikitenko, Nicolas Dacheux, Thomas Dumas, Adel Mesbah, Philippe Moisy, Matthieu Virot, Damien Prieur, Xavier F. Le Goff, Christoph Hennig, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interfaces de Matériaux en Evolution (LIME), Centre d'élaboration de matériaux et d'études structurales (CEMES), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), JRC Institute for Transuranium Elements [Karlsruhe] (ITU ), European Commission - Joint Research Centre [Karlsruhe] (JRC), Etude de la Matière en Mode Environnemental (L2ME), Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Service de Chimie des Procédés de Séparation (SCPS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, Ligand, Organic Chemistry, Thorium, chemistry.chemical_element, General Chemistry, Crystal structure, Structure type, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Peroxide, Catalysis, Synchrotron, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Crystallography, chemistry, law, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM]Chemical Sciences, Orthorhombic crystal system, Sulfate, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

International audience; The preparation and structural characterization of an original Th peroxo sulfate dihydrate, crystallizing at room temperature in the form of stable 1D polymeric microfibres is described. A combination of laboratory and synchrotron techniques allowed solution of the structure of the Th(O2)(SO4)(H2O)2 compound, which crystallizes in a new structure type in the space group Pna21 of the orthorhombic crystal system. Particularly, the peroxide ligand coordinates to the Th cations in an unusual μ3‐η2:η2:η2 bridging mode, forming an infinite 1D chain decorated with sulfato ligands exhibiting simultaneously monodentate and bidentate coordination modes.

Published
2019
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50. Microsensing of plutonium with a glass optofluidic device

Author

Philippe Moisy, Davide Bucci, Fabrice Canto, Fabien Geoffray, Timothee Allenet, Jean-Emmanuel Broquin, Institut de Microélectronique, Electromagnétisme et Photonique - Laboratoire d'Hyperfréquences et Caractérisation (IMEP-LAHC ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Detection limit, Materials science, Borosilicate glass, business.industry, Calibration curve, Microfluidics, General Engineering, chemistry.chemical_element, 02 engineering and technology, Chip, 01 natural sciences, Atomic and Molecular Physics, and Optics, Optofluidics, Plutonium, 010309 optics, [SPI.ELEC]Engineering Sciences [physics]/Electromagnetism, 020210 optoelectronics & photonics, chemistry, 0103 physical sciences, 0202 electrical engineering, electronic engineering, information engineering, [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, Optoelectronics, Absorption (electromagnetic radiation), business, ComputingMilieux_MISCELLANEOUS
Abstract

The cointegration of optical and microfluidic functions on chemically resilient borosilicate glass to provide microfluidic chemical analyses is described. An evanescent wave sensing chip containing a fluid channel of 21 μL is implemented to carry out absorption spectroscopy measurements in the near-infrared range. Microchip packaging allows to perform remote analysis of harsh chemical solutions in confined environments. Detection of plutonium(VI) in aqueous 1 mol/L nitric acid solutions is achieved on solutions ranging from 0.05 to 0.13 mol/L. Results showcase the validity of the proposed approach by obtaining a sensor calibration curve and chip resilience to highly concentrated strong acids and radioactive elements. This proof-of-concept opens the path to optimized devices with a lower limit of detection.

Published
2019
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