Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

Popa, Karin; Martel, Laura; Martin, Philippe M.; Prieur, Damien; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J.M.; Somers, Joseph

doi:10.1016/J.JSSC.2015.07.002

Title: Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

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Abstract

PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis of room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.

Authors:

Popa, Karin ^[1]; Martel, Laura ^[1]; Martin, Philippe M. ^[2]; Prieur, Damien ^[1]; Solari, Pier L. ^[3]; Bouëxière, Daniel; Konings, Rudy J.M.; Somers, Joseph ^[1]

European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany)
CEA, DEN, DEC/SESC, F-13108 Saint Paul Lez Durance Cedex (France)
Synchrotron SOLEIL, 91190 Saint-Aubin (France)

Publication Date:: Thu Oct 15 00:00:00 EDT 2015

OSTI Identifier:: 22486803

Resource Type:: Journal Article

Journal Name:: Journal of Solid State Chemistry

Additional Journal Information:: Journal Volume: 230; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CRYSTAL STRUCTURE; MONAZITES; NMR SPECTRA; PHOSPHORUS 31; PLUTONIUM PHOSPHATES; POWDERS; RESOLUTION; SOLID SOLUTIONS; SOLIDS; TEMPERATURE RANGE 0273-0400 K; VALENCE; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY

Citation Formats


                    Popa, Karin, Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu, Martel, Laura, Martin, Philippe M., Prieur, Damien, Solari, Pier L., Bouëxière, Daniel, Konings, Rudy J.M., and Somers, Joseph. Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy.  United States: N. p., 2015. 
        Web.  doi:10.1016/J.JSSC.2015.07.002.

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                    Popa, Karin, Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu, Martel, Laura, Martin, Philippe M., Prieur, Damien, Solari, Pier L., Bouëxière, Daniel, Konings, Rudy J.M., & Somers, Joseph. Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy.  United States.  https://doi.org/10.1016/J.JSSC.2015.07.002

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                    Popa, Karin, Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu, Martel, Laura, Martin, Philippe M., Prieur, Damien, Solari, Pier L., Bouëxière, Daniel, Konings, Rudy J.M., and Somers, Joseph. 2015.  
        "Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy".  United States.  https://doi.org/10.1016/J.JSSC.2015.07.002.

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@article{osti_22486803,

  title        = {Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy},

  author       = {Popa, Karin and Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu and Martel, Laura and Martin, Philippe M. and Prieur, Damien and Solari, Pier L. and Bouëxière, Daniel and Konings, Rudy J.M. and Somers, Joseph},

  abstractNote = {PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis of room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.},

  doi          = {10.1016/J.JSSC.2015.07.002},

  url          = {https://www.osti.gov/biblio/22486803},
  journal      = {Journal of Solid State Chemistry},

  issn         = {0022-4596},

  number       = ,

  volume       = 230,

  place        = {United States},

  year         = {Thu Oct 15 00:00:00 EDT 2015},

  month        = {Thu Oct 15 00:00:00 EDT 2015}

}

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