skip to main content

DOE PAGESDOE PAGES

Title: New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid

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:
 [1] ; ORCiD logo [2] ;  [3]
  1. 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
  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; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. 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:
Report Number(s):
LA-UR-18-28721
Journal ID: ISSN 2075-163X; MBSIBI
Grant/Contract Number:
89233218CNA000001; SC0001089; SC0016568
Type:
Accepted Manuscript
Journal Name:
Minerals
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2075-163X
Publisher:
MDPI
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranium(VI); phosphite; piperazinium; hydrothermal redox; crystal structures
OSTI Identifier:
1492676

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., 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. doi:10.3390/min8110497.
Villa, Eric M., Cross, Justin Neil, and Albrecht-Schmitt, Thomas E.. 2018. "New Uranyl Open Framework and Sheet Compounds Formed via In-Situ Protonation of Piperazine by Phosphorous Acid". United States. doi: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 = {2018},
month = {11}
}

Works referenced in this record:

Crystal structure refinement with SHELXL
journal, January 2015
  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

SHELXT � Integrated space-group and crystal-structure determination
journal, January 2015
  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370