From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates

Justin N. Cross; Patrick M. Duncan; Eric M. Villa; Matthew J. Polinski; Jean Marie Babo; Evgeny V. Alekseev; Corwin H. Booth; Thomas E. Albrecht-Schmitt

doi:10.1021/ja311910h

From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates

Justin N. Cross, Patrick M. Duncan, Eric M. Villa, Matthew J. Polinski, Jean Marie Babo, Evgeny V. Alekseev, Corwin H. Booth, Thomas E. Albrecht-Schmitt

Department of Chemistry

Research output: Contribution to journal › Article

25 Scopus citations

Abstract

Hydrothermal reactions of CeCl₃ and PuCl₃ with MoO₃ and Cs₂CO₃ yield surprisingly different results. Ce₃Mo₆O₂₄(H₂O)₄ crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å³), whereas CsPu₃Mo₆O ₂₄(H₂O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å³). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O₈ square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs⁺ in its channels, while the channels in Ce₃Mo₆O₂₄(H ₂O)₄ contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu₃Mo₆O ₂₄(H₂O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu₃Mo ₆O₂₄(H₂O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

Original language	English (US)
Pages (from-to)	2769-2775
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	135
Issue number	7
DOIs	https://doi.org/10.1021/ja311910h
State	Published - Feb 20 2013

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja311910h

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Cross, J. N., Duncan, P. M., Villa, E. M., Polinski, M. J., Babo, J. M., Alekseev, E. V., Booth, C. H., & Albrecht-Schmitt, T. E. (2013). From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates. Journal of the American Chemical Society, 135(7), 2769-2775. https://doi.org/10.1021/ja311910h

From yellow to black : Dramatic changes between cerium(IV) and plutonium(IV) molybdates. / Cross, Justin N.; Duncan, Patrick M.; Villa, Eric M.; Polinski, Matthew J.; Babo, Jean Marie; Alekseev, Evgeny V.; Booth, Corwin H.; Albrecht-Schmitt, Thomas E.

In: Journal of the American Chemical Society, Vol. 135, No. 7, 20.02.2013, p. 2769-2775.

Research output: Contribution to journal › Article

@article{c25ad466fef642c68758e1fd0a1eca10,

title = "From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates",

abstract = "Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) {\AA}, b = 22.1309(16) {\AA}, c = 7.8392(4) {\AA}, β = 96.591(4), V = 2194.6(2) {\AA}3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) {\AA}, b = 21.770(8) {\AA}, c = 7.743(7) {\AA}, β = 96.218(2), V = 2117(2) {\AA}3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).",

author = "Cross, {Justin N.} and Duncan, {Patrick M.} and Villa, {Eric M.} and Polinski, {Matthew J.} and Babo, {Jean Marie} and Alekseev, {Evgeny V.} and Booth, {Corwin H.} and Albrecht-Schmitt, {Thomas E.}",

year = "2013",

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T1 - From yellow to black

T2 - Dramatic changes between cerium(IV) and plutonium(IV) molybdates

AU - Cross, Justin N.

AU - Duncan, Patrick M.

AU - Villa, Eric M.

AU - Polinski, Matthew J.

AU - Babo, Jean Marie

AU - Alekseev, Evgeny V.

AU - Booth, Corwin H.

AU - Albrecht-Schmitt, Thomas E.

PY - 2013/2/20

Y1 - 2013/2/20

N2 - Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

AB - Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

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