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Title: Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate

Abstract

The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR spectroscopy, SEM-EDS, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O2(NO3)2·2H2O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Finally, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.

Authors:
 [1];  [2];  [2];  [2];  [3];  [1];  [4]
  1. State Univ. of New York (SUNY), Buffalo, NY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Texas A & M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1798329
Grant/Contract Number:  
AC02-06CH11357; NE0008653; SC0001136
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 2021; Journal Issue: 23; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yu, Xiaojuan, Einkauf, Jeffrey, Bryantsev, Vyacheslav S., Cheshire, Michael C., Reinhart, Benjamin J., Autschbach, Jochen, and Burns, Jonathan D.. Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate. United States: N. p., 2021. Web. https://doi.org/10.1039/D1CP01047.
Yu, Xiaojuan, Einkauf, Jeffrey, Bryantsev, Vyacheslav S., Cheshire, Michael C., Reinhart, Benjamin J., Autschbach, Jochen, & Burns, Jonathan D.. Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate. United States. https://doi.org/10.1039/D1CP01047
Yu, Xiaojuan, Einkauf, Jeffrey, Bryantsev, Vyacheslav S., Cheshire, Michael C., Reinhart, Benjamin J., Autschbach, Jochen, and Burns, Jonathan D.. Thu . "Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate". United States. https://doi.org/10.1039/D1CP01047.
@article{osti_1798329,
title = {Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate},
author = {Yu, Xiaojuan and Einkauf, Jeffrey and Bryantsev, Vyacheslav S. and Cheshire, Michael C. and Reinhart, Benjamin J. and Autschbach, Jochen and Burns, Jonathan D.},
abstractNote = {The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR spectroscopy, SEM-EDS, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O2(NO3)2·2H2O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Finally, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.},
doi = {10.1039/D1CP01047},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 23,
volume = 2021,
place = {United States},
year = {2021},
month = {5}
}

Journal Article:
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This content will become publicly available on May 13, 2022
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