Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface
Abstract
The differential capacitance as a function of potential and composition for choline chloride (ChCl) and ethylene glycol (EG) at 1:2, 1:4, 1:6, and 1:20 molar ratios were studied using electrochemical impedance spectroscopy (EIS) on glassy carbon. In addition, ChCl:EG at the known ethaline DES composition (1:2) and 1:20 molar ratio were studied on Au and Pt electrodes, and compared to glyceline (ChCl:glycerol, 1:2). The capacitance-potential curves on glassy carbon were best interpreted by the modified Gouy-Chapman model. A dampened U-shape was observed similar to dilute electrolytes, however, the non-negligible ionic and H-bonding interactions in these electrolytes resulted in ambiguity about the point of zero charge where capacitance was weakly dependent on potential. Additionally, the differential capacitance was independent of composition on glassy carbon due to limited availability of mobile free ions and constraints by solvated ion sizes within the interface. Increases in capacitance are observed with Au as a result of desolvation and specific adsorption of Cl, and with Pt upon decreased Cl concentrations. These results indicate DESs and H-bonded electrolytes with high salt concentrations are distinct from ionic liquids and present no pronounced overscreening or crowding with applied potential.
- Authors:
- Publication Date:
- Research Org.:
- Case Western Reserve Univ., Cleveland, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1832947
- Alternate Identifier(s):
- OSTI ID: 1808448
- Grant/Contract Number:
- SC0019409
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 168 Journal Issue: 2; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Dean, William, Klein, Jeffrey, and Gurkan, Burcu. Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface. United States: N. p., 2021.
Web. doi:10.1149/1945-7111/abde83.
Dean, William, Klein, Jeffrey, & Gurkan, Burcu. Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface. United States. https://doi.org/10.1149/1945-7111/abde83
Dean, William, Klein, Jeffrey, and Gurkan, Burcu. Tue .
"Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface". United States. https://doi.org/10.1149/1945-7111/abde83.
@article{osti_1832947,
title = {Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface},
author = {Dean, William and Klein, Jeffrey and Gurkan, Burcu},
abstractNote = {The differential capacitance as a function of potential and composition for choline chloride (ChCl) and ethylene glycol (EG) at 1:2, 1:4, 1:6, and 1:20 molar ratios were studied using electrochemical impedance spectroscopy (EIS) on glassy carbon. In addition, ChCl:EG at the known ethaline DES composition (1:2) and 1:20 molar ratio were studied on Au and Pt electrodes, and compared to glyceline (ChCl:glycerol, 1:2). The capacitance-potential curves on glassy carbon were best interpreted by the modified Gouy-Chapman model. A dampened U-shape was observed similar to dilute electrolytes, however, the non-negligible ionic and H-bonding interactions in these electrolytes resulted in ambiguity about the point of zero charge where capacitance was weakly dependent on potential. Additionally, the differential capacitance was independent of composition on glassy carbon due to limited availability of mobile free ions and constraints by solvated ion sizes within the interface. Increases in capacitance are observed with Au as a result of desolvation and specific adsorption of Cl, and with Pt upon decreased Cl concentrations. These results indicate DESs and H-bonded electrolytes with high salt concentrations are distinct from ionic liquids and present no pronounced overscreening or crowding with applied potential.},
doi = {10.1149/1945-7111/abde83},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 168,
place = {United States},
year = {Tue Feb 02 00:00:00 EST 2021},
month = {Tue Feb 02 00:00:00 EST 2021}
}
https://doi.org/10.1149/1945-7111/abde83
Works referenced in this record:
Liquid structure of the choline chloride-urea deep eutectic solvent (reline) from neutron diffraction and atomistic modelling
journal, January 2016
- Hammond, Oliver S.; Bowron, Daniel T.; Edler, Karen J.
- Green Chemistry, Vol. 18, Issue 9
Differential capacitance of the double layer at the electrode/ionic liquids interface
journal, January 2010
- Lockett, Vera; Horne, Mike; Sedev, Rossen
- Physical Chemistry Chemical Physics, Vol. 12, Issue 39
On the temperature dependence of the double layer capacitance of ionic liquids
journal, June 2018
- Chen, Ming; Goodwin, Zachary A. H.; Feng, Guang
- Journal of Electroanalytical Chemistry, Vol. 819
Sur la constitution de la charge électrique à la surface d'un électrolyte
journal, January 1910
- Gouy, M.
- Journal de Physique Théorique et Appliquée, Vol. 9, Issue 1
Potential dependent capacitance of [EMIM][TFSI], [N 1114 ][TFSI] and [PYR 13 ][TFSI] ionic liquids on glassy carbon
journal, January 2019
- Klein, Jeffrey M.; Panichi, Evio; Gurkan, Burcu
- Physical Chemistry Chemical Physics, Vol. 21, Issue 7
Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations
journal, January 2017
- Goodwin, Zachary A. H.; Feng, Guang; Kornyshev, Alexei A.
- Electrochimica Acta, Vol. 225
Liquid Structure and Transport Properties of the Deep Eutectic Solvent Ethaline
journal, May 2020
- Zhang, Yong; Poe, Derrick; Heroux, Luke
- The Journal of Physical Chemistry B, Vol. 124, Issue 25
Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality
journal, December 2019
- Klein, Jeffrey M.; Squire, Henry; Gurkan, Burcu
- The Journal of Physical Chemistry C, Vol. 124, Issue 10
Correction to “Double-Layer in Ionic Liquids: Paradigm Change?”
journal, October 2013
- Kornyshev, A. A.
- The Journal of Physical Chemistry B, Vol. 117, Issue 44
Electrochemical studies of gold and chloride in ionic liquids
journal, January 2006
- Aldous, Leigh; Silvester, Debbie S.; Villagrán, Constanza
- New J. Chem., Vol. 30, Issue 11
Hysteresis effects and roughness suppression efficacy of polyethylenimine additive in Cu electrodeposition in ethaline
journal, June 2020
- Shaheen, Nora A.; Mahesh, Ijjada; Vukmirovic, Miomir B.
- Electrochemistry Communications, Vol. 115
From Salt in Solution to Solely Ions: Solvation of Methyl Viologen in Deep Eutectic Solvents and Ionic Liquids
journal, June 2020
- Klein, Jeffrey M.; Squire, Henry; Dean, William
- The Journal of Physical Chemistry B, Vol. 124, Issue 29
Differential capacity of a deep eutectic solvent based on choline chloride and glycerol on solid electrodes
journal, March 2009
- Figueiredo, Marta; Gomes, Cristiana; Costa, Renata
- Electrochimica Acta, Vol. 54, Issue 9
Quaternary Ammonium Cation Specific Adsorption on Platinum Electrodes: A Combined Experimental and Density Functional Theory Study
journal, January 2018
- McCrum, I. T.; Hickner, M. A.; Janik, M. J.
- Journal of The Electrochemical Society, Vol. 165, Issue 2
Extraction desulfurization process of fuels with ammonium-based deep eutectic solvents
journal, January 2013
- Li, Changping; Li, Dan; Zou, Shuangshuang
- Green Chemistry, Vol. 15, Issue 10
On Capacitive Processes at the Interface between 1-Ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and Au(111)
journal, March 2011
- Drüschler, Marcel; Huber, Benedikt; Roling, Bernhard
- The Journal of Physical Chemistry C, Vol. 115, Issue 14
Influence of additives on the electrodeposition of zinc from a deep eutectic solvent
journal, May 2019
- Alesary, Hasan F.; Cihangir, Salih; Ballantyne, Andrew D.
- Electrochimica Acta, Vol. 304
A Sustainable Redox-Flow Battery with an Aluminum-Based, Deep-Eutectic-Solvent Anolyte
journal, May 2017
- Zhang, Changkun; Ding, Yu; Zhang, Leyuan
- Angewandte Chemie International Edition, Vol. 56, Issue 26
Metal-Free Deep Eutectic Solvents: Preparation, Physical Properties, and Significance
journal, November 2019
- Gurkan, Burcu; Squire, Henry; Pentzer, Emily
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 24
Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids
journal, July 2004
- Abbott, Andrew P.; Boothby, David; Capper, Glen
- Journal of the American Chemical Society, Vol. 126, Issue 29
Double Layer in Ionic Liquids: Overscreening versus Crowding
journal, January 2011
- Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A.
- Physical Review Letters, Vol. 106, Issue 4
A Gouy–Chapman–Stern model of the double layer at a (metal)/(ionic liquid) interface
journal, February 2008
- Oldham, Keith B.
- Journal of Electroanalytical Chemistry, Vol. 613, Issue 2
Nanostructure of Deep Eutectic Solvents at Graphite Electrode Interfaces as a Function of Potential
journal, January 2016
- Chen, Zhengfei; McLean, Ben; Ludwig, Michael
- The Journal of Physical Chemistry C, Vol. 120, Issue 4