Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices

摘要: Author(s): Burton-Pye, BP; Dembowski, M; Lukens, WW; Cruz, A; Althour, Lopez, GE; Salcedo, R; Gallagher, CMB; McGregor, D; Francesconi, LC | Abstract: © 2019 WILEY-VCH Verlag GmbH a Co. KGaA, Weinheim Technetium-99, prevalent by-product of the nuclear fuel cycle, is transition metal with 9 accessible oxidation states and half-life 2.1 × 105 years. 99TcVII has been found in environment surrounding National Lab sites reprocessing centers, its separation long-term storage complicated by extensive redox chemistry. In our prior work we have reported synthesis reduction TcVO to TcIVO α1- α2-Wells–Dawson P2W17O6110– polyoxometalates on polyoxometalate features that promote stabilization. this report state stabilization TcVO, TcVIO TcVIN within α-Keggin PW11O397– polyoxometalate. Both Density Functional Theory experimental results show Tc TBA4[TcVIN-PW11O39] can be reduced TcV, but any subsequent electrons reduce tungsten framework TBA4[TcVO-PW11O39] however, theoretically down TcI before occurs.