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]

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• 作者：René Bès ; Murielle Rivenet ; Pier-Lorenzo Solari ; Kristina O. Kvashnina ; Andreas C. Scheinost ; Philippe M. Martin
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4260-4270
• 全文大小：648K
• 年卷期：0
• ISSN：1520-510X

文摘

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 2p_3/2–5f 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.