Trace Water Changes Metal Ion Speciation in Deep Eutectic Solvents : Ce3+ Solvation and Nanoscale Water Clustering in Choline Chloride-Urea-Water Mixtures
Hammond, Oliver S. ; Bathke, Elly K. LU ; Bowron, Daniel T. and Edler, Karen J. LU
(2023)
In Inorganic Chemistry
62(44).
p.18069-18078
- Abstract
Eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES)/water molar hydration ratios (w) of 2, 5, and 10, with dissolved cerium salt, were measured using neutron diffraction with isotopic substitution. Structures were modeled using empirical potential structure refinement (EPSR). Ce3+ was found to form highly charged complexes with a mean coordination number between 7 and 8, with the shell containing mostly chloride, followed by water. The shell composition is strongly affected by the molar ratio of dilution, as opposed to the mass or volume fraction, due to the high affinity of Cl- and H2O ligands that displace less favorable interactions with ligands such as urea and... (More)
Eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES)/water molar hydration ratios (w) of 2, 5, and 10, with dissolved cerium salt, were measured using neutron diffraction with isotopic substitution. Structures were modeled using empirical potential structure refinement (EPSR). Ce3+ was found to form highly charged complexes with a mean coordination number between 7 and 8, with the shell containing mostly chloride, followed by water. The shell composition is strongly affected by the molar ratio of dilution, as opposed to the mass or volume fraction, due to the high affinity of Cl- and H2O ligands that displace less favorable interactions with ligands such as urea and choline. The presence of Ce3+ salt disrupted the bulk DES structure slightly, making it more electrolyte-like. The measured coordination shell of choline showed significant discrepancies from the statistical noninteracting distribution, highlighting the nonideality of the blend. Cluster analysis revealed the trace presence of percolating water clusters (25 ≥ n ≥ 2) in solvent compositions of 5 and 10w for the first time.
(Less)
- author
- Hammond, Oliver S.
; Bathke, Elly K.
LU
; Bowron, Daniel T.
and Edler, Karen J.
LU
- publishing date
- 2023-11-06
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Inorganic Chemistry
- volume
- 62
- issue
- 44
- pages
- 10 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:37862703
- scopus:85176499021
- ISSN
- 0020-1669
- DOI
- 10.1021/acs.inorgchem.3c02205
- language
- English
- LU publication?
- no
- id
- cf12fbf9-66ec-4b6a-80f9-c9ba48ed2d9c
- date added to LUP
- 2023-11-24 14:28:44
- date last changed
- 2024-04-21 17:18:47
@article{cf12fbf9-66ec-4b6a-80f9-c9ba48ed2d9c,
abstract = {{<p>Eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES)/water molar hydration ratios (w) of 2, 5, and 10, with dissolved cerium salt, were measured using neutron diffraction with isotopic substitution. Structures were modeled using empirical potential structure refinement (EPSR). Ce<sup>3+</sup> was found to form highly charged complexes with a mean coordination number between 7 and 8, with the shell containing mostly chloride, followed by water. The shell composition is strongly affected by the molar ratio of dilution, as opposed to the mass or volume fraction, due to the high affinity of Cl<sup>-</sup> and H<sub>2</sub>O ligands that displace less favorable interactions with ligands such as urea and choline. The presence of Ce<sup>3+</sup> salt disrupted the bulk DES structure slightly, making it more electrolyte-like. The measured coordination shell of choline showed significant discrepancies from the statistical noninteracting distribution, highlighting the nonideality of the blend. Cluster analysis revealed the trace presence of percolating water clusters (25 ≥ n ≥ 2) in solvent compositions of 5 and 10w for the first time.</p>}},
author = {{Hammond, Oliver S. and Bathke, Elly K. and Bowron, Daniel T. and Edler, Karen J.}},
issn = {{0020-1669}},
language = {{eng}},
month = {{11}},
number = {{44}},
pages = {{18069--18078}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Inorganic Chemistry}},
title = {{Trace Water Changes Metal Ion Speciation in Deep Eutectic Solvents : Ce<sup>3+</sup> Solvation and Nanoscale Water Clustering in Choline Chloride-Urea-Water Mixtures}},
url = {{http://dx.doi.org/10.1021/acs.inorgchem.3c02205}},
doi = {{10.1021/acs.inorgchem.3c02205}},
volume = {{62}},
year = {{2023}},
}