Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Radivojevic Jovanovic, Ivana; Gallagher, Colleen B.; Salcedo, Ramsey; Lukens, Wayne W.; Burton-Pye, Benjamin P.; McGregor, Donna; Francesconi, Lynn C.

doi:10.1002/ejic.202000170

Title: Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Journal Article · Mon May 11 00:00:00 EDT 2020 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.202000170· OSTI ID:1685051

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City Univ. of New York (CUNY), NY (United States).
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Technetium-99 (half-life of 2.1 × 10⁵ yrs, β_max = 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. Here, 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 (XW₁₂O₄₀^n–) (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 Tc^IV {in the form of TcO₂·2H₂O and Tc₂(µ-O)₂⁴⁺} and Tc^V, which is subsequently complexed into a POM defect as a Tc^V=O species.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; FG‐09ER16097; AC02‐76SF00515; HRD‐1547830; DGE‐0965983; CHE‐0750118

OSTI ID:: 1685051

Alternate ID(s):: OSTI ID: 1617987

Journal Information:: European Journal of Inorganic Chemistry, Vol. 2020, Issue 22; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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