Photoreduction of {sup 99}Tc Pertechnetate by Nanometer-Sized Metal Oxides: New Strategies for Formation and Sequestration of Low-Valent Technetium (open access)

Photoreduction of {sup 99}Tc Pertechnetate by Nanometer-Sized Metal Oxides: New Strategies for Formation and Sequestration of Low-Valent Technetium

Technetium-99 ({sup 99}Tc) ({beta}{sup -}{sub max}: 293.7 keV; t{sub 1/2}: 2.1 x 10{sup 5} 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 (TcO{sub 4}{sup -}) is stable. TcO{sub 4}{sup -} 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), {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-}, that can be photoactivated in the presence of 2-propanol to transfer electrons to TcO{sub 4}{sup -}, and incorporate the reduced Tc covalently into the {alpha}2- framework to form the Tc{sup V}O species, Tc{sup V}O({alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}){sup 7-}. This occurs via the formation of an intermediate species that slowly converts to Tc{sup V}O({alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}){sup 7-}. EXAFS and XANES analysis and preliminary EPR analysis, suggests that the intermediate consists of a Tc(IV) {alpha}2- species where the Tc is likely bound to only 2 of the 4 W-O oxygen atoms in …
Date: July 4, 2011
Creator: Burton-Pye, Benjamin P.; Radivojevic, Ivana; McGregor, Donna; Mbomekalle, Israel M.; Lukens, Jr., Wayne W. & Francesconi, Lynn C.
System: The UNT Digital Library