New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid
Abstract
Two new uranyl compounds were hydrothermally synthesized employing piperazine as an organic templating agent. The piperazine was protonated in-situ by phosphorous acid, forming the piperazinium dication featured in these compounds. The two new structures presented here are a uranyl phosphite 2D sheet and a 3D uranyl mixed phosphite–phosphate network with cation occupied channels. Both included strong hydrogen bonding from the piperazinium cation to the uranyl phosphite or mixed phosphite–phosphate network. These two structures can be reliably formed through careful control of pH of the starting solution and the reaction duration. The piperazinium uranyl phosphite compound was the latest in a family of uranyl phosphites, and demonstrates the structural versatility of this combination. Finally, the mixed phosphite–phosphate compound builds on hydrothermal redox chemistry, illustrating the variety of compounds that can be isolated by exploiting in-situ redox processes to elucidate new uranium structure types.
- Authors:
-
[2];
- Univ. of Notre Dame, IN (United States). Dept. of Civil Engineering and Geological Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry; Creighton Univ., Omaha, NB (United States). Dept. of Chemistry
- Univ. of Notre Dame, IN (United States). Dept. of Civil Engineering and Geological Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of Notre Dame, IN (United States). Dept. of Civil Engineering and Geological Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry; Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST). Materials Science of Actinides (MSA); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1492676
- Report Number(s):
- LA-UR-18-28721
Journal ID: ISSN 2075-163X; MBSIBI
- Grant/Contract Number:
- 89233218CNA000001; SC0001089; SC0016568
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Minerals
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2075-163X
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranium(VI); phosphite; piperazinium; hydrothermal redox; crystal structures
Citation Formats
Villa, Eric M., Cross, Justin Neil, and Albrecht-Schmitt, Thomas E. New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid. United States: N. p., 2018.
Web. doi:10.3390/min8110497.
Villa, Eric M., Cross, Justin Neil, & Albrecht-Schmitt, Thomas E. New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid. United States. https://doi.org/10.3390/min8110497
Villa, Eric M., Cross, Justin Neil, and Albrecht-Schmitt, Thomas E. Thu .
"New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid". United States. https://doi.org/10.3390/min8110497. https://www.osti.gov/servlets/purl/1492676.
@article{osti_1492676,
title = {New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid},
author = {Villa, Eric M. and Cross, Justin Neil and Albrecht-Schmitt, Thomas E.},
abstractNote = {Two new uranyl compounds were hydrothermally synthesized employing piperazine as an organic templating agent. The piperazine was protonated in-situ by phosphorous acid, forming the piperazinium dication featured in these compounds. The two new structures presented here are a uranyl phosphite 2D sheet and a 3D uranyl mixed phosphite–phosphate network with cation occupied channels. Both included strong hydrogen bonding from the piperazinium cation to the uranyl phosphite or mixed phosphite–phosphate network. These two structures can be reliably formed through careful control of pH of the starting solution and the reaction duration. The piperazinium uranyl phosphite compound was the latest in a family of uranyl phosphites, and demonstrates the structural versatility of this combination. Finally, the mixed phosphite–phosphate compound builds on hydrothermal redox chemistry, illustrating the variety of compounds that can be isolated by exploiting in-situ redox processes to elucidate new uranium structure types.},
doi = {10.3390/min8110497},
journal = {Minerals},
number = 11,
volume = 8,
place = {United States},
year = {Thu Nov 01 00:00:00 EDT 2018},
month = {Thu Nov 01 00:00:00 EDT 2018}
}
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Figures / Tables:
Table 1: Table of crystallographic data for listed compounds: [H2PZ][UO2(HPO3)2] (1) and [(H2PZ)Cs][(UO2)2(HPO3)2(PO4)] (2).
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Uranyl Coordination Compounds with Alkaline Earth Metals and Crotonate Ligands
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