Synthesis and Characterization of Non‐Aqueous [Tc X M‐PW 11 O 39 ] n – with M = O, N: Comparing Tc V and Tc VI in Metal Oxide Matrices
| Autor: | Lynn C. Francesconi, Mateusz Dembowski, Alrasheed Althour, Colleen M. B. Gallagher, Anthony Cruz, Gustavo E. López, Donna McGregor, Benjamin P. Burton-Pye, Ramsey Salcedo, Wayne W. Lukens |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Oxide chemistry.chemical_element Tungsten 010402 general chemistry 01 natural sciences Redox 0104 chemical sciences Inorganic Chemistry Metal chemistry.chemical_compound Transition metal chemistry Oxidation state visual_art Polyoxometalate visual_art.visual_art_medium Physical chemistry Density functional theory |
| Zdroj: | European Journal of Inorganic Chemistry. 2019:4826-4834 |
| ISSN: | 1099-0682 1434-1948 |
| Popis: | Author(s): Burton-Pye, BP; Dembowski, M; Lukens, WW; Cruz, A; Althour, A; Lopez, GE; Salcedo, R; Gallagher, CMB; McGregor, D; Francesconi, LC | Abstract: Technetium-99, a prevalent by-product of the nuclear fuel cycle, is a transition metal with 9 accessible oxidation states and a half-life of 2.1 × 105 years. 99TcVII has been found in the environment surrounding National Lab sites and fuel reprocessing centers, and its separation and long-term storage is complicated by its extensive redox chemistry. In our prior work we have reported the synthesis and reduction of TcVO to TcIVO in α1- and α2-Wells–Dawson P2W17O6110– polyoxometalates and reported on the polyoxometalate features that promote reduction and stabilization. In this work we report on the oxidation state stabilization of TcVO, TcVIO and TcVIN within the α-Keggin PW11O397– polyoxometalate. Both Density Functional Theory and experimental results show that Tc in TBA4[TcVIN-PW11O39] can be reduced to TcV, but any subsequent electrons reduce the tungsten framework of the polyoxometalate. TBA4[TcVO-PW11O39] however, can be theoretically reduced down to TcI before reduction of the polyoxometalate occurs. |
| Databáze: | OpenAIRE |
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