Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices
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 × 10 5 years. 99 Tc VII 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 Tc V O to Tc IV O in α 1 ‐ and α 2 ‐Wells–Dawson P 2 W 17 O 61 10– polyoxometalates and reported on the polyoxometalate features that promote reduction and stabilization. In this work we report on the oxidation state stabilization of Tc V O, Tc VI O and Tc VI N within the α‐Keggin PW 11 O 39 7– polyoxometalate. Both Density Functional Theory and experimental results show that Tc in TBA 4 [Tc VI N‐PW 11 O 39 ] can be reduced to Tc V , but any subsequent electrons reduce the tungsten framework of the polyoxometalate. TBA 4 [Tc V O‐PW 11 O 39 ] however, can be theoretically reduced down to Tc I before reduction of the polyoxometalate occurs.
- Authors:
-
[1];
[2];
[3];
[1];
[5];
[1];
[6]
- City Univ. of New York (CUNY), NY (United States). Lehman College; City Univ. of New York (CUNY), NY (United States). Ph.D. Program in Chemistry Graduate Center
- City Univ. of New York (CUNY), NY (United States). Hunter College
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Div., The Glenn T. Seaborg Center
- City Univ. of New York (CUNY), NY (United States). Lehman College
- City Univ. of New York (CUNY), NY (United States). Lehman College; City Univ. of New York (CUNY), NY (United States). Ph.D. Program in Chemistry Graduate Center; City Univ. of New York (CUNY), NY (United States). Hunter College
- City Univ. of New York (CUNY), NY (United States). Ph.D. Program in Chemistry Graduate Center; City Univ. of New York (CUNY), NY (United States). Hunter College
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1782133
- Alternate Identifier(s):
- OSTI ID: 1575837
- Grant/Contract Number:
- AC02-05CH11231; HRD-1547830; DGE-0965983; CHE-0750118; FG‐09ER16097
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2019; Journal Issue: 45; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Burton‐Pye, Benjamin P., Dembowski, Mateusz, Lukens, Wayne W., Cruz, Anthony, Althour, Alrasheed, Lopez, Gustavo E., Salcedo, Ramsey, Gallagher, Colleen B., McGregor, Donna, and Francesconi, Lynn C. Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices. United States: N. p., 2019.
Web. doi:10.1002/ejic.201900864.
Burton‐Pye, Benjamin P., Dembowski, Mateusz, Lukens, Wayne W., Cruz, Anthony, Althour, Alrasheed, Lopez, Gustavo E., Salcedo, Ramsey, Gallagher, Colleen B., McGregor, Donna, & Francesconi, Lynn C. Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices. United States. https://doi.org/10.1002/ejic.201900864
Burton‐Pye, Benjamin P., Dembowski, Mateusz, Lukens, Wayne W., Cruz, Anthony, Althour, Alrasheed, Lopez, Gustavo E., Salcedo, Ramsey, Gallagher, Colleen B., McGregor, Donna, and Francesconi, Lynn C. Tue .
"Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices". United States. https://doi.org/10.1002/ejic.201900864. https://www.osti.gov/servlets/purl/1782133.
@article{osti_1782133,
title = {Synthesis and Characterization of Non-Aqueous [TcXM-PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices},
author = {Burton‐Pye, Benjamin P. and Dembowski, Mateusz and Lukens, Wayne W. and Cruz, Anthony and Althour, Alrasheed and Lopez, Gustavo E. and Salcedo, Ramsey and Gallagher, Colleen B. and McGregor, Donna and Francesconi, Lynn C.},
abstractNote = {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 × 10 5 years. 99 Tc VII 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 Tc V O to Tc IV O in α 1 ‐ and α 2 ‐Wells–Dawson P 2 W 17 O 61 10– polyoxometalates and reported on the polyoxometalate features that promote reduction and stabilization. In this work we report on the oxidation state stabilization of Tc V O, Tc VI O and Tc VI N within the α‐Keggin PW 11 O 39 7– polyoxometalate. Both Density Functional Theory and experimental results show that Tc in TBA 4 [Tc VI N‐PW 11 O 39 ] can be reduced to Tc V , but any subsequent electrons reduce the tungsten framework of the polyoxometalate. TBA 4 [Tc V O‐PW 11 O 39 ] however, can be theoretically reduced down to Tc I before reduction of the polyoxometalate occurs.},
doi = {10.1002/ejic.201900864},
journal = {European Journal of Inorganic Chemistry},
number = 45,
volume = 2019,
place = {United States},
year = {Tue Nov 26 00:00:00 EST 2019},
month = {Tue Nov 26 00:00:00 EST 2019}
}
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