Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]

Tutkimustuotos: Lehtiartikkeli

Standard

Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]. / Bès, René; Rivenet, Murielle; Solari, Pier Lorenzo; Kvashnina, Kristina O.; Scheinost, Andreas C.; Martin, Philippe M.

julkaisussa: Inorganic Chemistry, Vuosikerta 55, Nro 9, 02.05.2016, s. 4260-4270.

Tutkimustuotos: Lehtiartikkeli

Harvard

Bès, R, Rivenet, M, Solari, PL, Kvashnina, KO, Scheinost, AC & Martin, PM 2016, 'Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]', Inorganic Chemistry, Vuosikerta. 55, Nro 9, Sivut 4260-4270. https://doi.org/10.1021/acs.inorgchem.6b00014

APA

Vancouver

Author

Bès, René ; Rivenet, Murielle ; Solari, Pier Lorenzo ; Kvashnina, Kristina O. ; Scheinost, Andreas C. ; Martin, Philippe M. / Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]. Julkaisussa: Inorganic Chemistry. 2016 ; Vuosikerta 55, Nro 9. Sivut 4260-4270.

Bibtex - Lataa

@article{a196f0060eaf4b0e9ea27a0f6d1c4bed,
title = "Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]",
abstract = "We report and discuss here the unambiguous uranium valence state determination on the complex compound [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] by using high-energy-resolution fluorescence detection-X-ray absorption near-edge structure spectroscopy (HERFD-XANES). The spectra at both U L3- and M4-edges confirm that all five nonequivalent U atoms are solely in the hexavalent form in this compound, as previously suggested by bond-valence-sum analysis and X-ray diffraction pattern refinement. Moreover, the presence of the preedge feature, due to the 2p3/2-5f quadrupole transition, has been observed in the U L3-edge HERFD-XANES spectrum, in agreement with theoretical and experimental observations of other uranium-based compounds. Recently, this feature has been proposed as a possible tool to determine the uranium oxidation state in a manner similar to that of 3d and 4d metals. Nevertheless, this feature is also very sensitive to the uranium local environment, as revealed by our theoretical calculations, and consequently could not be used to attribute without ambiguity the uranium valence state. In contrast, U M4-edge HERFD-XANES appears to be the most straightforward and reliable way to assess the uranium valence state in very complex materials such as [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] or a mixture of compounds.",
author = "Ren{\'e} B{\`e}s and Murielle Rivenet and Solari, {Pier Lorenzo} and Kvashnina, {Kristina O.} and Scheinost, {Andreas C.} and Martin, {Philippe M.}",
year = "2016",
month = "5",
day = "2",
doi = "10.1021/acs.inorgchem.6b00014",
language = "English",
volume = "55",
pages = "4260--4270",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "AMERICAN CHEMICAL SOCIETY",
number = "9",

}

RIS - Lataa

TY - JOUR

T1 - Use of HERFD-XANES at the U L3- and M4-Edges to Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3]

AU - Bès, René

AU - Rivenet, Murielle

AU - Solari, Pier Lorenzo

AU - Kvashnina, Kristina O.

AU - Scheinost, Andreas C.

AU - Martin, Philippe M.

PY - 2016/5/2

Y1 - 2016/5/2

N2 - We report and discuss here the unambiguous uranium valence state determination on the complex compound [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] by using high-energy-resolution fluorescence detection-X-ray absorption near-edge structure spectroscopy (HERFD-XANES). The spectra at both U L3- and M4-edges confirm that all five nonequivalent U atoms are solely in the hexavalent form in this compound, as previously suggested by bond-valence-sum analysis and X-ray diffraction pattern refinement. Moreover, the presence of the preedge feature, due to the 2p3/2-5f quadrupole transition, has been observed in the U L3-edge HERFD-XANES spectrum, in agreement with theoretical and experimental observations of other uranium-based compounds. Recently, this feature has been proposed as a possible tool to determine the uranium oxidation state in a manner similar to that of 3d and 4d metals. Nevertheless, this feature is also very sensitive to the uranium local environment, as revealed by our theoretical calculations, and consequently could not be used to attribute without ambiguity the uranium valence state. In contrast, U M4-edge HERFD-XANES appears to be the most straightforward and reliable way to assess the uranium valence state in very complex materials such as [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] or a mixture of compounds.

AB - We report and discuss here the unambiguous uranium valence state determination on the complex compound [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] by using high-energy-resolution fluorescence detection-X-ray absorption near-edge structure spectroscopy (HERFD-XANES). The spectra at both U L3- and M4-edges confirm that all five nonequivalent U atoms are solely in the hexavalent form in this compound, as previously suggested by bond-valence-sum analysis and X-ray diffraction pattern refinement. Moreover, the presence of the preedge feature, due to the 2p3/2-5f quadrupole transition, has been observed in the U L3-edge HERFD-XANES spectrum, in agreement with theoretical and experimental observations of other uranium-based compounds. Recently, this feature has been proposed as a possible tool to determine the uranium oxidation state in a manner similar to that of 3d and 4d metals. Nevertheless, this feature is also very sensitive to the uranium local environment, as revealed by our theoretical calculations, and consequently could not be used to attribute without ambiguity the uranium valence state. In contrast, U M4-edge HERFD-XANES appears to be the most straightforward and reliable way to assess the uranium valence state in very complex materials such as [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] or a mixture of compounds.

UR - http://www.scopus.com/inward/record.url?scp=84968796704&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.6b00014

DO - 10.1021/acs.inorgchem.6b00014

M3 - Article

VL - 55

SP - 4260

EP - 4270

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 9

ER -

ID: 27629488