U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4

Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang; Solomon, Jonathan M.; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Kukkadapu, Ravi K.; Wu, Di; Ilton, Eugene S.; Asta, Mark; Sutton, Stephen R.; Xu, Hongwu; Navrotsky, Alexandra

doi:10.1039/C6DT00066E

Title: U(v) in metal uranates: A combined experimental and theoretical study of MgUO₄, CrUO₄, and FeUO₄

Abstract

Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO₄, CrUO₄ and FeUO₄ were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57Fe-Mossbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U⁵⁺ has been solidly confirmed in CrUO₄ and FeUO₄, which are thermodynamically stable compounds, and the origin and stability of U⁵⁺ in the system was elaborated by DFT. Lastly, the structural and thermodynamic behaviour of U⁵⁺ elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.

Authors:

Guo, Xiaofeng ^[1]; Tiferet, Eitan ^[2]; Qi, Liang ^[3]; Solomon, Jonathan M. ^[4]; Lanzirotti, Antonio ^[5]; Newville, Matthew ^[5]; Engelhard, Mark H. ^[6]; Kukkadapu, Ravi K. ^[6]; Wu, Di ^[7]; Ilton, Eugene S. ^[6]; Asta, Mark ^[4]; Sutton, Stephen R. ^[5]; Xu, Hongwu ^[8]; Navrotsky, Alexandra ^[7]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Negev Be'er-Sheva (Israel)
Univ. of California, Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of Chicago, Chicago, IL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of California, Davis, CA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Tue Feb 02 00:00:00 EST 2016

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1256103

Report Number(s):: LA-UR-15-28081
Journal ID: ISSN 1477-9226; ICHBD9

Grant/Contract Number:: AC52-06NA25396; SC0001089

Resource Type:: Accepted Manuscript

Journal Name:: Dalton Transactions

Additional Journal Information:: Journal Volume: 45; Journal Issue: 11; Journal ID: ISSN 1477-9226

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Inorganic and Physical Chemistry; Material Science; uranium; uranate; X-ray absorption spectroscopy; X-ray photoelectron spectroscopy; calorimetry; structure; DFT

Citation Formats


                    Guo, Xiaofeng, Tiferet, Eitan, Qi, Liang, Solomon, Jonathan M., Lanzirotti, Antonio, Newville, Matthew, Engelhard, Mark H., Kukkadapu, Ravi K., Wu, Di, Ilton, Eugene S., Asta, Mark, Sutton, Stephen R., Xu, Hongwu, and Navrotsky, Alexandra. U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4.  United States: N. p., 2016. 
Web.  doi:10.1039/C6DT00066E.

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                    Guo, Xiaofeng, Tiferet, Eitan, Qi, Liang, Solomon, Jonathan M., Lanzirotti, Antonio, Newville, Matthew, Engelhard, Mark H., Kukkadapu, Ravi K., Wu, Di, Ilton, Eugene S., Asta, Mark, Sutton, Stephen R., Xu, Hongwu, & Navrotsky, Alexandra. U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4.  United States.  https://doi.org/10.1039/C6DT00066E

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                    Guo, Xiaofeng, Tiferet, Eitan, Qi, Liang, Solomon, Jonathan M., Lanzirotti, Antonio, Newville, Matthew, Engelhard, Mark H., Kukkadapu, Ravi K., Wu, Di, Ilton, Eugene S., Asta, Mark, Sutton, Stephen R., Xu, Hongwu, and Navrotsky, Alexandra. Tue .  
"U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4".  United States.  https://doi.org/10.1039/C6DT00066E.  https://www.osti.gov/servlets/purl/1256103.

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@article{osti_1256103,

  title        = {U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4},

  author       = {Guo, Xiaofeng and Tiferet, Eitan and Qi, Liang and Solomon, Jonathan M. and Lanzirotti, Antonio and Newville, Matthew and Engelhard, Mark H. and Kukkadapu, Ravi K. and Wu, Di and Ilton, Eugene S. and Asta, Mark and Sutton, Stephen R. and Xu, Hongwu and Navrotsky, Alexandra},

  abstractNote = {Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO4, CrUO4 and FeUO4 were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57Fe-Mossbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U5+ has been solidly confirmed in CrUO4 and FeUO4, which are thermodynamically stable compounds, and the origin and stability of U5+ in the system was elaborated by DFT. Lastly, the structural and thermodynamic behaviour of U5+ elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.},

  doi          = {10.1039/C6DT00066E},

  journal      = {Dalton Transactions},

  number       = 11,

  volume       = 45,

  place        = {United States},

  year         = {Tue Feb 02 00:00:00 EST 2016},

  month        = {Tue Feb 02 00:00:00 EST 2016}

}

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Influence of crystal structure and chemical composition on the energy transfer processes in uranates

Journal Article Krol, D M ; Ros, J P.M. ; Roos, A - J. Chem. Phys.; (United States)

The luminescence properties of several uranates are reported. The compounds that have been investigated are Y/sub 6/UO/sub 12/, Li/sub 4/UO/sub 5/, Li/sub 2/UO/sub 4/, and MgUO/sub 4/, all of which contain distorted uranate octahedra. Emission and excitation spectra and the quantum efficiency of the luminescence were measured at 4.2 K. Furthermore, the temperature dependence of the luminescence was investigated. The results show that the excitation energy migrates through the lattice and that the luminescence occurs from uranate centers near defects. These centers act as traps for the migrating excitation energy. The quantum efficiency of the luminescence varies strongly within thismore »« less
https://doi.org/10.1063/1.440304

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Title: U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4

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Citation Formats

Some Uranium-Transition Element Double Oxides book, June 1967

Thermochemistry of uranium compounds VIII. Standard enthalpies of formation at 298.15 K of the uranates of calcium (CaUO4) and barium (BaUO4). Thermodynamics of the behavior of barium in nuclear fuels journal, September 1976

Chemistry of uranium (V) journal, October 1969

Chemistry of Aqueous Uranium(V) Solutions. II. Reaction of Uranium Pentachloride with Water. Thermodynamic Stability of UO 2 + . Potential of U(IV)/(V), U(IV)/(VI) and U(V)/(VI) Couples journal, July 1949

The preparation and spectrum of uranium(V) ions in aqueous solutions journal, November 1970

The system Cr2O3UO2O2 journal, December 1962

Magnetoelectric compounds with two sets of magnetic sublattices: UCrO4 and NdCrTiO5 journal, August 1974

Thermochemistry of uranium compounds IX. Standard enthalpy of formation and high-temperature thermodynamic functions of magnesium uranate (MgUO4) A comment on the non-existence of beryllium uranate journal, October 1977

X-ray photoelectron spectroscopy of alkaline earth metal uranate complexes journal, December 1978

Electron spin resonance spectra of mixed oxides containing uranium and alkaline earth metals journal, January 1978

The standard enthalpies of formation of uranium compounds. XV. Strontium uranates journal, October 1999

The Local Uranium Environment in Cesium Uranates: A Combined XPS, XAS, XRD, and Neutron Diffraction Analysis journal, July 2002

Thermodynamics of uranyl minerals: Enthalpies of formation of uranyl oxide hydrates journal, April 2006

Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis journal, January 2007

XPS spectra of the compounds , and journal, May 2009

XPS determination of uranium oxidation states: XPS determination of uranium oxidation states journal, October 2011

Studies in the System MgUO3-MgUO4 journal, January 1964

Crystal chemical studies of the 5 f -series of elements. XXI. The crystal structure of magnesium orthouranate journal, December 1954

The stoichiometric magnesium, calcium, strontium and barium monouranates journal, December 1974

Observations on reactions of uranium compounds journal, December 1959

X-ray Data for the Chrome-Urania System, Cr2O3·2UO3 journal, December 1961

Magnetic Structures and Properties of UFeO 4 journal, March 1969

Projector augmented-wave method journal, December 1994

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

Generalized Gradient Approximation Made Simple journal, October 1996

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Crystal chemical studies of the 5 f -series of elements. IV. The crystal structure of Ca(UO 2 )O 2 and Sr(UO 2 )O 2 journal, December 1948

Speciation of Uranium in Sediments before and after In situ Biostimulation journal, March 2008

Pentavalent Uranium Oxide via Reduction of [UO 2 ] 2+ Under Hydrothermal Reaction Conditions † journal, November 2008

Oxidation State Delineation via U L III -Edge XANES in a Series of Isostructural Uranium Coordination Complexes journal, April 2012

Energetics of Ternary Nitrides: Li−Ca−Zn−N and Ca−Ta−N Systems journal, July 1997

Thermodynamics of formation of coffinite, USiO 4 journal, May 2015

Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics journal, December 2013

An acidity scale for binary oxides journal, June 1987

Thermochemistry of microporous silicotitanate phases in the Na 2 O–Cs 2 O–SiO 2 –TiO 2 –H 2 O system journal, March 2000

Crystal chemistry and energetics of pharmacosiderite-related microporous phases in the K2O–Cs2O–SiO2–TiO2–H2O system journal, July 2004

Perovskite Solid Solutions along the NaNbO 3 −SrTiO 3 Join: Phase Transitions, Formation Enthalpies, and Implications for General Perovskite Energetics journal, April 2005

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr) journal, August 2005

Thermodynamics of thorium substitution in yttrium iron garnet: comparison of experimental and theoretical results journal, January 2014

Formation enthalpies of LaLn׳O3 (Ln׳=Ho, Er, Tm and Yb) interlanthanide perovskites journal, July 2015

Charge-Coupled Substituted Garnets (Y 3– x Ca 0.5 x M 0.5 x )Fe 5 O 12 (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms journal, March 2015

Synthesis, characterization and thermochemistry of Cs-, Rb- and Sr-substituted barium aluminium titanate hollandites journal, April 2015

A profile refinement method for nuclear and magnetic structures journal, June 1969

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal, June 2005

Pertechnetate (TcO4−) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA journal, September 2012

Special points for Brillouin-zone integrations journal, June 1976

Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of Li x FePO 4 journal, October 2006

Rotationally invariant ab initio evaluation of Coulomb and exchange parameters for DFT+U calculations journal, July 2008

Hybrid density functional theory band structure engineering in hematite journal, June 2011

High-pressure characteristics of α-Fe 2 O 3 using DFT+ U journal, January 2005

Formation enthalpies by mixing GGA and GGA + U calculations journal, July 2011

Oxidation energies of transition metal oxides within the GGA + U framework journal, May 2006

Computational study of the energetics and defect clustering tendencies for Y- and La-doped UO2 journal, October 2014

Computational study of the energetics of charge and cation mixing in U 1 − x Ce x O 2 journal, August 2011

Progress and new directions in high temperature calorimetry revisited journal, April 1997

Enthalpies of formation of Ce-pyrochlore, Ca0.93Ce1.00Ti2.035O7.00, U-pyrochlore, Ca1.46U4+0.23U6+0.46Ti1.85O7.00 and Gd-pyrochlore, Gd2Ti2O7: three materials relevant to the proposed waste form for excess weapons plutonium journal, June 2002

Energetics of metastudtite and implications for nuclear waste alteration journal, November 2014

Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite journal, March 2018

Direct observation of pure pentavalent uranium in U2O5 thin films by high resolution photoemission spectroscopy journal, May 2018

Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO 2 journal, April 2019

Title: U(v) in metal uranates: A combined experimental and theoretical study of MgUO₄, CrUO₄, and FeUO₄

Some Uranium-Transition Element Double Oxides
book, June 1967

Thermochemistry of uranium compounds VIII. Standard enthalpies of formation at 298.15 K of the uranates of calcium (CaUO4) and barium (BaUO4). Thermodynamics of the behavior of barium in nuclear fuels
journal, September 1976

Chemistry of uranium (V)
journal, October 1969

Chemistry of Aqueous Uranium(V) Solutions. II. Reaction of Uranium Pentachloride with Water. Thermodynamic Stability of UO ₂ ⁺ . Potential of U(IV)/(V), U(IV)/(VI) and U(V)/(VI) Couples
journal, July 1949

The preparation and spectrum of uranium(V) ions in aqueous solutions
journal, November 1970

The system Cr2O3UO2O2
journal, December 1962

Magnetoelectric compounds with two sets of magnetic sublattices: UCrO4 and NdCrTiO5
journal, August 1974

Thermochemistry of uranium compounds IX. Standard enthalpy of formation and high-temperature thermodynamic functions of magnesium uranate (MgUO4) A comment on the non-existence of beryllium uranate
journal, October 1977

X-ray photoelectron spectroscopy of alkaline earth metal uranate complexes
journal, December 1978

Electron spin resonance spectra of mixed oxides containing uranium and alkaline earth metals
journal, January 1978

The standard enthalpies of formation of uranium compounds. XV. Strontium uranates
journal, October 1999

The Local Uranium Environment in Cesium Uranates: A Combined XPS, XAS, XRD, and Neutron Diffraction Analysis
journal, July 2002

Thermodynamics of uranyl minerals: Enthalpies of formation of uranyl oxide hydrates
journal, April 2006

Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis
journal, January 2007

XPS spectra of the compounds , and
journal, May 2009

XPS determination of uranium oxidation states: XPS determination of uranium oxidation states
journal, October 2011

Studies in the System MgUO3-MgUO4
journal, January 1964

Crystal chemical studies of the 5 f -series of elements. XXI. The crystal structure of magnesium orthouranate
journal, December 1954

The stoichiometric magnesium, calcium, strontium and barium monouranates
journal, December 1974

Observations on reactions of uranium compounds
journal, December 1959

X-ray Data for the Chrome-Urania System, Cr2O3·2UO3
journal, December 1961

Magnetic Structures and Properties of UFeO ₄
journal, March 1969

Projector augmented-wave method
journal, December 1994

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Generalized Gradient Approximation Made Simple
journal, October 1996

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Crystal chemical studies of the 5 f -series of elements. IV. The crystal structure of Ca(UO ₂ )O ₂ and Sr(UO ₂ )O ₂
journal, December 1948

Speciation of Uranium in Sediments before and after In situ Biostimulation
journal, March 2008

Pentavalent Uranium Oxide via Reduction of [UO ₂ ] ²⁺ Under Hydrothermal Reaction Conditions ^†
journal, November 2008

Oxidation State Delineation via U L _III -Edge XANES in a Series of Isostructural Uranium Coordination Complexes
journal, April 2012

Energetics of Ternary Nitrides: Li−Ca−Zn−N and Ca−Ta−N Systems
journal, July 1997

Thermodynamics of formation of coffinite, USiO ₄
journal, May 2015

Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics
journal, December 2013

An acidity scale for binary oxides
journal, June 1987

Thermochemistry of microporous silicotitanate phases in the Na ₂ O–Cs ₂ O–SiO ₂ –TiO ₂ –H ₂ O system
journal, March 2000

Crystal chemistry and energetics of pharmacosiderite-related microporous phases in the K2O–Cs2O–SiO2–TiO2–H2O system
journal, July 2004

Perovskite Solid Solutions along the NaNbO ₃ −SrTiO ₃ Join: Phase Transitions, Formation Enthalpies, and Implications for General Perovskite Energetics
journal, April 2005

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr)
journal, August 2005

Thermodynamics of thorium substitution in yttrium iron garnet: comparison of experimental and theoretical results
journal, January 2014

Formation enthalpies of LaLn׳O3 (Ln׳=Ho, Er, Tm and Yb) interlanthanide perovskites
journal, July 2015

Charge-Coupled Substituted Garnets (Y _{3– x} Ca _{0.5 x} M _{0.5 x} )Fe ₅ O ₁₂ (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms
journal, March 2015

Synthesis, characterization and thermochemistry of Cs-, Rb- and Sr-substituted barium aluminium titanate hollandites
journal, April 2015

A profile refinement method for nuclear and magnetic structures
journal, June 1969

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Pertechnetate (TcO4−) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA
journal, September 2012

Special points for Brillouin-zone integrations
journal, June 1976

Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of ${Li}_{x} {FePO}_{4}$
journal, October 2006

Rotationally invariant ab initio evaluation of Coulomb and exchange parameters for DFT+U calculations
journal, July 2008

Hybrid density functional theory band structure engineering in hematite
journal, June 2011

High-pressure characteristics of α-Fe ₂ O ₃ using DFT+ U
journal, January 2005

Formation enthalpies by mixing GGA and GGA $+$ $U$ calculations
journal, July 2011

Oxidation energies of transition metal oxides within the $GGA + U$ framework
journal, May 2006

Computational study of the energetics and defect clustering tendencies for Y- and La-doped UO2
journal, October 2014

Computational study of the energetics of charge and cation mixing in U $_{1 - x}$ Ce $_{x}$ O $_{2}$
journal, August 2011

Progress and new directions in high temperature calorimetry revisited
journal, April 1997

Enthalpies of formation of Ce-pyrochlore, Ca0.93Ce1.00Ti2.035O7.00, U-pyrochlore, Ca1.46U4+0.23U6+0.46Ti1.85O7.00 and Gd-pyrochlore, Gd2Ti2O7: three materials relevant to the proposed waste form for excess weapons plutonium
journal, June 2002

Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014

Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite
journal, March 2018

Direct observation of pure pentavalent uranium in U2O5 thin films by high resolution photoemission spectroscopy
journal, May 2018

Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO ₂
journal, April 2019