The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments
Abstract
Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K+ salts from crude solids of the monomer building block UO2(O2)34– (K–U1), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K+ salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K6[(UO2)2(O2)4(OH)2]·7H2O (K–U2) and a hexamer face frequently observed in the capsules, K12[(UO2)6(O2)9(OH)6]$·x$H2O(K–U6). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U1 (days) < K–U2 (hours) < K–U6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control themore »
- Authors:
-
[2];
[3];
[2];
[1]
- Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
- Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Inst.
- Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
- Publication Date:
- Research Org.:
- Univ. of Notre Dame, IN (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1593800
- Grant/Contract Number:
- NA0003763
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 3; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Arteaga, Ana, Ray, Debmalya, Glass, Elliot, Martin, Nicolas P., Zakharov, Lev N., Gagliardi, Laura, and Nyman, May. The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.9b02660.
Arteaga, Ana, Ray, Debmalya, Glass, Elliot, Martin, Nicolas P., Zakharov, Lev N., Gagliardi, Laura, & Nyman, May. The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments. United States. https://doi.org/10.1021/acs.inorgchem.9b02660
Arteaga, Ana, Ray, Debmalya, Glass, Elliot, Martin, Nicolas P., Zakharov, Lev N., Gagliardi, Laura, and Nyman, May. Tue .
"The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments". United States. https://doi.org/10.1021/acs.inorgchem.9b02660. https://www.osti.gov/servlets/purl/1593800.
@article{osti_1593800,
title = {The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments},
author = {Arteaga, Ana and Ray, Debmalya and Glass, Elliot and Martin, Nicolas P. and Zakharov, Lev N. and Gagliardi, Laura and Nyman, May},
abstractNote = {Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K+ salts from crude solids of the monomer building block UO2(O2)34– (K–U1), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K+ salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K6[(UO2)2(O2)4(OH)2]·7H2O (K–U2) and a hexamer face frequently observed in the capsules, K12[(UO2)6(O2)9(OH)6]$·x$H2O(K–U6). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U1 (days) < K–U2 (hours) < K–U6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.},
doi = {10.1021/acs.inorgchem.9b02660},
journal = {Inorganic Chemistry},
number = 3,
volume = 59,
place = {United States},
year = {Tue Jan 21 00:00:00 EST 2020},
month = {Tue Jan 21 00:00:00 EST 2020}
}
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