Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates

Shuao Wang, Eric Villa, Juan Diwu, Evgeny V. Alekseev, Wulf Depmeier, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

U(VI), Np(VI), and Pu(VI) borates with the formula AnO2[B 8O11(OH)4] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO22+, surrounded by BO 3 triangles and BO4 tetrahedra to create an AnO 8 hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO3 triangles and BO4 tetrahedra extend from the polyborate layers and connect these sheets together toform a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

Original languageEnglish
Pages (from-to)2527-2533
Number of pages7
JournalInorganic Chemistry
Volume50
Issue number6
DOIs
StatePublished - Mar 21 2011
Externally publishedYes

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Neptunium
neptunium
Plutonium
Borates
Uranium
plutonium
borates
triangles
tetrahedrons
Nitrates
uranium
Anions
nitrates
Actinoid Series Elements
anions
boric acids
preparation
Fluorescence spectroscopy
Bond length
perchlorates

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates. / Wang, Shuao; Villa, Eric; Diwu, Juan; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

In: Inorganic Chemistry, Vol. 50, No. 6, 21.03.2011, p. 2527-2533.

Research output: Contribution to journalArticle

Wang, Shuao ; Villa, Eric ; Diwu, Juan ; Alekseev, Evgeny V. ; Depmeier, Wulf ; Albrecht-Schmitt, Thomas E. / Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 6. pp. 2527-2533.
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AU - Alekseev, Evgeny V.

AU - Depmeier, Wulf

AU - Albrecht-Schmitt, Thomas E.

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N2 - U(VI), Np(VI), and Pu(VI) borates with the formula AnO2[B 8O11(OH)4] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO22+, surrounded by BO 3 triangles and BO4 tetrahedra to create an AnO 8 hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO3 triangles and BO4 tetrahedra extend from the polyborate layers and connect these sheets together toform a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

AB - U(VI), Np(VI), and Pu(VI) borates with the formula AnO2[B 8O11(OH)4] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO22+, surrounded by BO 3 triangles and BO4 tetrahedra to create an AnO 8 hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO3 triangles and BO4 tetrahedra extend from the polyborate layers and connect these sheets together toform a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

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