Technetium-99 (99Tc) (?-max: 293.7 keV; t?: 2.1 x 105 years) is a byproduct of uranium-235 fission and comprises a large component of radioactive waste. Under aerobic conditions and in a neutral- basic environment, the pertechnetate anion (TcO4-) is stable. TcO4- is very soluble, migrates easily through the environment and does not sorb well onto mineral surfaces, soils or sediments. This study moves forward a new strategy for the reduction of TcO4- and chemical incorporation of the reduced Tc into a metal oxide material. This strategy employs a single material, a polyoxometalate (POM), ?2-[P2W17O61]10-, that can be photoactivated in the presence of 2-propanol to transfer electrons to TcO4-, and incorporate the reduced Tc covalently into the ?2- framework to form the TcVO species, TcVO(?2-P2W17O61)7-. This occurs via the formation of an intermediate species that slowly converts to TcVO(?2-P2W17O61)7-. EXAFS and XANES analysis and preliminary EPR analysis, suggests that the intermediate consists of a Tc(IV) ?2- species where the Tc is likely bound to only 2 of the 4 W-O oxygen atoms in the ?2-[P2W17O61]10- defect. This intermediate then oxidizes and converts to the TcVO(?2-P2W17O61)7- product. The reduction and incorporation of TcO4- was accomplished in a ?one pot? reaction using both sunlight and UV irradiation, and monitored as a function of time using multinuclear NMR and radio TLC. The process was further probed by the ?step-wise? generation of reduced ?2-P2W17O6112- through bulk electrolysis followed by the addition of TcO4-. The reduction and incorporation of ReO4-, as a non-radioactive surrogate for 99Tc, does not proceed through the intermediate species, and ReVO is incorporated quickly into the ?2-[P2W17O61]10- defect. These observations are consistent with the periodic trends of Tc and Re. Specifically, Tc is more easily reduced compared to Re. In addition to serving as models for metal oxides, POMs may also provide a suitable platform to study the molecular level dynamics and mechanisms of the reduction and incorporation of Tc into a material.

Synthesis of technetium-99 (99Tc; t1/2: 2.1 105 years, max: 253 keV) materials is of importance in studies of the nuclear fuel cycle where Tc is a major fission product (6percent thermal yield from 235U and 239Pu), in understanding radioactive tank waste composition, and in identifying 99mTc compounds for nuclear medicine imaging. One of the most useful synthetic starting materials, (NBu4)TcOCl4, is susceptible to disproportionation in water to form TcO4 and TcIV species, especially TcO2 2H2O. This unwanted reaction is especially problematic when working with ligands bearing hard donor atoms, such as oxygen, where the stability with the soft TcV=O3+ core may be low. Polyoxometalates (POMs) are such ligands. They possess defect sites with four hard oxygen atoms and show low (ca. 108) stability constants with transition metals. Tc complexes of POMs are molecular-level models for Tc metal oxide solid-state materials and can provide information on coordination and redox environments of metal oxides that stabilize low-valent Tc. In order to synthesize pure Tc POM complexes [TcVO(1-P2W17O61)]7 (TcVO-1) and [TcVO(2-P2W17O61)]7 (TcVO-2) from (NBu4)TcOCl4, we have identified strategies that minimize formation of TcIV species and optimize the formation of pure TcV species. The parameters that we consider are the amount of ethylene glycol, which is employed as a transfer ligand to prevent hydrolysis of (NBu4)TcOCl4, and the precipitating agent. The TcIV species that contaminates the non-optimized syntheses is likely a TcIV -oxido-bridged dimer [TcIV-(-O)2-TcIV]. We also employ a novel procedure where the 2 ligand is photoactivated and reduced (in the presence of a sacrificial electron donor) to subsequently reduce TcVIIO4 to an isolatable TcVO-2 product that is remarkably free of TcIV.

Technetium-99 (half-life of 2.1 × 105 yrs, βmax = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO4–), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α2-[P2W17O61]10–) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW12O40n–) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO4– and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW12, SiW12, and AlW12 promote the reduction of TcO4– to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of TcIV {in the form of TcO2·2H2O and Tc2(µ-O)24+} and TcV, which is subsequently complexed into a POM defect as a TcV=O species.

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.