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

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

doi:10.1021/ic102356d

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

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

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

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 language	English (US)
Pages (from-to)	2527-2533
Number of pages	7
Journal	Inorganic Chemistry
Volume	50
Issue number	6
DOIs	https://doi.org/10.1021/ic102356d
State	Published - Mar 21 2011
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{e15309f6541c4d668994a4d4835ce5f4,

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

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).",

author = "Shuao Wang and Villa, {Eric M.} and Juan Diwu and Alekseev, {Evgeny V.} and Wulf Depmeier and Albrecht-Schmitt, {Thomas E.}",

year = "2011",

month = mar,

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language = "English (US)",

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journal = "Inorganic Chemistry",

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T1 - Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates

AU - Wang, Shuao

AU - Villa, Eric M.

AU - Diwu, Juan

AU - Alekseev, Evgeny V.

AU - Depmeier, Wulf

AU - Albrecht-Schmitt, Thomas E.

PY - 2011/3/21

Y1 - 2011/3/21

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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