Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction
Abstract
We report that separation of U, Np, and Pu from used nuclear fuel (UNF) would result in lower long-term radiotoxicity, alleviating constraints on the storage and handling of the material. The complexity of UNF requires several industrial-scale processes with multiple waste streams. A one-step solution to the group removal of the elements, U–Pu, is desirable. Here we present a possible solution to group actinide separation utilizing the unique dioxy conformation of An(V/VI) cations and demonstrate the ability of a tetradentate lipophilic Schiff base ligand (L) to yield isostructural complexes of the general formula [(AnVIO2)(L)(CH3CN)] (where An = U, Np, or Pu). Extraction of An(VI) with the ligand follows the order U > Pu > Np, likely reflecting the decreased stability of the hexavalent actinide across the series. Lastly, while the results indicate a promising path toward a one-step process, further improvement in the ligand stability and control of the redox chemistry is required.
- Authors:
-
[3];
[3];
[3];
[4]
- Univ. of California, Irvine, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Tennessee Technological Univ., Cookeville, TN (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of California, Irvine, CA (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1499366
- Report Number(s):
- LA-UR-19-21331
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 6; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bustillos, Christian G., Hawkins, Cory A., Copping, Roy, Reilly, Sean Douglas, Scott, Brian Lindley, May, Iain, and Nilsson, Mikael. Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.8b02849.
Bustillos, Christian G., Hawkins, Cory A., Copping, Roy, Reilly, Sean Douglas, Scott, Brian Lindley, May, Iain, & Nilsson, Mikael. Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction. United States. https://doi.org/10.1021/acs.inorgchem.8b02849
Bustillos, Christian G., Hawkins, Cory A., Copping, Roy, Reilly, Sean Douglas, Scott, Brian Lindley, May, Iain, and Nilsson, Mikael. Tue .
"Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction". United States. https://doi.org/10.1021/acs.inorgchem.8b02849. https://www.osti.gov/servlets/purl/1499366.
@article{osti_1499366,
title = {Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction},
author = {Bustillos, Christian G. and Hawkins, Cory A. and Copping, Roy and Reilly, Sean Douglas and Scott, Brian Lindley and May, Iain and Nilsson, Mikael},
abstractNote = {We report that separation of U, Np, and Pu from used nuclear fuel (UNF) would result in lower long-term radiotoxicity, alleviating constraints on the storage and handling of the material. The complexity of UNF requires several industrial-scale processes with multiple waste streams. A one-step solution to the group removal of the elements, U–Pu, is desirable. Here we present a possible solution to group actinide separation utilizing the unique dioxy conformation of An(V/VI) cations and demonstrate the ability of a tetradentate lipophilic Schiff base ligand (L) to yield isostructural complexes of the general formula [(AnVIO2)(L)(CH3CN)] (where An = U, Np, or Pu). Extraction of An(VI) with the ligand follows the order U > Pu > Np, likely reflecting the decreased stability of the hexavalent actinide across the series. Lastly, while the results indicate a promising path toward a one-step process, further improvement in the ligand stability and control of the redox chemistry is required.},
doi = {10.1021/acs.inorgchem.8b02849},
journal = {Inorganic Chemistry},
number = 6,
volume = 58,
place = {United States},
year = {Tue Feb 26 00:00:00 EST 2019},
month = {Tue Feb 26 00:00:00 EST 2019}
}
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