Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

Klein, Jeffrey M.; Squire, Henry; Gurkan, Burcu

doi:10.1021/acs.jpcc.9b08016

Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

Journal Article · Thu Dec 12 04:00:00 EST 2019 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.9b08016· OSTI ID:1616162

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Case Western Reserve Univ., Cleveland, OH (United States); Case Western Reserve University
Case Western Reserve Univ., Cleveland, OH (United States)

The influence of ionic associations and potential-dependent interactions on the electrode–electrolyte interfacial structure of ionic liquids (ILs) is studied by electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) for a variety of asymmetric quaternary ammonium ILs. Specifically, the impact of cation alkyl chain length (C = 4, 8 and 16) and ether functionality on the interfacial structuring of ILs at the glassy carbon electrode surface is examined. Ammonium cations with alkyl chain length of 8 and 16 carbons are found to stabilize the formation of the bis(trifluorosulfonyl)imide, [TFSI], anion dense Stern layer at positive electrode potentials leading to larger capacitances. The longer alkyl chain of the cation is believed to screen the ion–ion repulsion among the anions by intruding into the interfacial anion layer. SERS suggests the presence of carbon-containing rings at the interface at both positive and negative electrode potentials, which can be explained by the buckling of the long alkyl chains. Inclusion of an ether functionality allowed for more symmetry in the camel-shaped potential-dependent differential capacitance curves, suggesting similar excess ion density at both positive and negative potentials. This work contributes to understanding and predicting the interfacial electrode capacitance in ILs by understanding the balance of ionic interactions and the associated repulsions at electrode–electrolyte interfaces that are pertinent to electrochemical energy storage, electrocatalysis, and electrochemical sensors.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Breakthrough Electrolytes for Energy Storage (BEES); Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0019409

OSTI ID:: 1616162

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 10 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Voltammetry in Room Temperature Ionic Liquids: Comparisons and Contrasts with Conventional Electrochemical Solvents. Barrosse-Antle, L. E.; Bond, A. M.; Compton, R. G. Chemistry - An Asian Journal, Vol. 5, Issue 2 https://doi.org/10.1002/asia.200900191	journal	February 2010
New Experimental Evidences Regarding Conformational Equilibrium in Ammonium−Bis(trifluoromethanesulfonyl)imide Ionic Liquids Gontrani, Lorenzo; Trequattrini, Francesco; Palumbo, Oriele ChemPhysChem, Vol. 19, Issue 20 https://doi.org/10.1002/cphc.201800442	journal	July 2018
Capacitive hysteresis at the 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate–polycrystalline gold interface Lucio, Anthony J.; Shaw, Scott K. Analytical and Bioanalytical Chemistry, Vol. 410, Issue 19 https://doi.org/10.1007/s00216-018-0962-5	journal	March 2018
Improved accessibility of porous carbon electrodes with surfactant ionic liquids for supercapacitors Xu, Ningjin; Klein, Jeffrey M.; Huang, Phoebe Journal of Applied Electrochemistry, Vol. 49, Issue 2 https://doi.org/10.1007/s10800-018-1266-3	journal	October 2018
Vibrational Stark effect of adsorbates at electrochemical interfaces Lambert, David K. Electrochimica Acta, Vol. 41, Issue 5 https://doi.org/10.1016/0013-4686(95)00349-5	journal	April 1996
Surface-enhanced Raman spectroscopy of amino acids adsorbed on an electrochemically prepared silver surface Stewart, S.; Fredericks, P. M. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 55, Issue 7-8 https://doi.org/10.1016/S1386-1425(98)00294-7	journal	July 1999
Applications of ionic liquids in electrochemical sensors Wei, Di; Ivaska, Ari Analytica Chimica Acta, Vol. 607, Issue 2 https://doi.org/10.1016/j.aca.2007.12.011	journal	January 2008
Ionic liquids as electrolytes Galiński, Maciej; Lewandowski, Andrzej; Stępniak, Izabela Electrochimica Acta, Vol. 51, Issue 26 https://doi.org/10.1016/j.electacta.2006.03.016	journal	August 2006
The influence of air and its components on the cathodic stability of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide Randström, S.; Appetecchi, G. B.; Lagergren, C. Electrochimica Acta, Vol. 53, Issue 4, p. 1837-1842 https://doi.org/10.1016/j.electacta.2007.08.029	journal	December 2007
Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations Goodwin, Zachary A. H.; Feng, Guang; Kornyshev, Alexei A. Electrochimica Acta, Vol. 225 https://doi.org/10.1016/j.electacta.2016.12.092	journal	January 2017
Measurements of the potential of zero charge in room temperature ionic liquids at Ag electrode by surface-enhanced Raman spectroscopy Liu, Yan; Yuan, Ya-Xian; Wang, Xin-Rong Journal of Electroanalytical Chemistry, Vol. 728 https://doi.org/10.1016/j.jelechem.2014.06.021	journal	August 2014
Probing double layer structure at Au/[BMIm]BF4 interface by molecular length-dependent SERS Stark effect Zhang, Na; Wang, Xing-Rong; Yuan, Ya-Xian Journal of Electroanalytical Chemistry, Vol. 751 https://doi.org/10.1016/j.jelechem.2015.05.041	journal	August 2015
On the temperature dependence of the double layer capacitance of ionic liquids Chen, Ming; Goodwin, Zachary A. H.; Feng, Guang Journal of Electroanalytical Chemistry, Vol. 819 https://doi.org/10.1016/j.jelechem.2017.11.005	journal	June 2018
Investigating the electrochemical windows of ionic liquids Hayyan, Maan; Mjalli, Farouq S.; Hashim, Mohd Ali Journal of Industrial and Engineering Chemistry, Vol. 19, Issue 1 https://doi.org/10.1016/j.jiec.2012.07.011	journal	January 2013
Ionic liquid dispersed Li+ ion oxide glasses and glass-ceramics: Assessment of electrical transport and thermal stability Rathore, Munesh; Dalvi, Anshuman; Kumar, Anil Solid State Ionics, Vol. 282 https://doi.org/10.1016/j.ssi.2015.09.028	journal	December 2015
Quantification of Halide in Ionic Liquids Using Ion Chromatography Villagrán, Constanza; Deetlefs, Maggel; Pitner, William R. Analytical Chemistry, Vol. 76, Issue 7 https://doi.org/10.1021/ac035157z	journal	April 2004
Interfacial Structure at the Quaternary Ammonium-Based Ionic Liquids\|Gold Electrode Interface Probed by Surface-Enhanced Infrared Absorption Spectroscopy: Anion Dependence of the Cationic Behavior Nishi, Naoya; Minami, Kazuya; Motobayashi, Kenta The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b10826	journal	January 2017
Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris The Journal of Physical Chemistry C, Vol. 122, Issue 19 https://doi.org/10.1021/acs.jpcc.8b02521	journal	April 2018
Relationships between Molecular Structure, Interfacial Structure, and Dynamics of Ionic Liquids near Neutral and Charged Surfaces Gil, Phwey S.; Jorgenson, Sara J.; Riet, Adriaan R. The Journal of Physical Chemistry C, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpcc.8b08644	journal	November 2018
Direct Measurement of the Differential Capacitance of Solvent-Free and Dilute Ionic Liquids Jitvisate, Monchai; Seddon, James R. T. The Journal of Physical Chemistry Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acs.jpclett.7b02946	journal	December 2017
Electrospinning Biopolymers from Ionic Liquids Requires Control of Different Solution Properties than Volatile Organic Solvents Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 6 https://doi.org/10.1021/acssuschemeng.7b00863	journal	May 2017
Surface Structure at the Ionic Liquid−Electrified Metal Interface Baldelli, Steven Accounts of Chemical Research, Vol. 41, Issue 3 https://doi.org/10.1021/ar700185h	journal	March 2008
Dye-Sensitized Solar Cells Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr900356p	journal	November 2010
Surface Layering in Ionic Liquids: An X-ray Reflectivity Study Sloutskin, Eli; Ocko, Benjamin M.; Tamam, Lilach Journal of the American Chemical Society, Vol. 127, Issue 21 https://doi.org/10.1021/ja0509679	journal	June 2005
Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures Tian, Zhong-Qun; Ren, Bin; Wu, De-Yin The Journal of Physical Chemistry B, Vol. 106, Issue 37 https://doi.org/10.1021/jp0257449	journal	September 2002
Electroreduction of Oxygen in a Series of Room Temperature Ionic Liquids Composed of Group 15-Centered Cations and Anions Evans, Russell G.; Klymenko, Oleksiy V.; Saddoughi, Sahar A. The Journal of Physical Chemistry B, Vol. 108, Issue 23 https://doi.org/10.1021/jp031309i	journal	June 2004
Raman Investigation of the Ionic Liquid N -Methyl- N -propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide and Its Mixture with LiN(SO ₂ CF ₃ ) ₂ Castriota, M.; Caruso, T.; Agostino, R. G. The Journal of Physical Chemistry A, Vol. 109, Issue 1 https://doi.org/10.1021/jp046030w	journal	January 2005
Application of Density Functional Theory and Vibrational Spectroscopy Toward the Rational Design of Ionic Liquids Katsyuba, Sergey A.; Zvereva, Elena E.; Vidiš, Ana The Journal of Physical Chemistry A, Vol. 111, Issue 2 https://doi.org/10.1021/jp064610i	journal	January 2007
Rapid and Accurate Estimation of Densities of Room-Temperature Ionic Liquids and Salts Ye, Chengfeng; Shreeve, Jean'ne M. The Journal of Physical Chemistry A, Vol. 111, Issue 8 https://doi.org/10.1021/jp066202k	journal	March 2007
Nanoscale Segregation in Room Temperature Ionic Liquids ^† Triolo, Alessandro; Russina, Olga; Bleif, Hans-Jurgen The Journal of Physical Chemistry B, Vol. 111, Issue 18 https://doi.org/10.1021/jp067705t	journal	May 2007
Double-Layer in Ionic Liquids: Paradigm Change? Kornyshev, Alexei A. The Journal of Physical Chemistry B, Vol. 111, Issue 20 https://doi.org/10.1021/jp067857o	journal	May 2007
Molecular Dynamics Simulation of the Ionic Liquid N -Ethyl- N,N -dimethyl- N -(2-methoxyethyl)ammonium Bis(trifluoromethanesulfonyl)imide Siqueira, Leonardo J. A.; Ribeiro, Mauro C. C. The Journal of Physical Chemistry B, Vol. 111, Issue 40 https://doi.org/10.1021/jp074840c	journal	October 2007
Molecular Simulations of the Electric Double Layer Structure, Differential Capacitance, and Charging Kinetics for N -Methyl- N -propylpyrrolidinium Bis(fluorosulfonyl)imide at Graphite Electrodes Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp2001207	journal	March 2011
On Capacitive Processes at the Interface between 1-Ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and Au(111) Drüschler, Marcel; Huber, Benedikt; Roling, Bernhard The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp200395j	journal	March 2011
Differential Capacitance of the Electrical Double Layer in Imidazolium-Based Ionic Liquids: Influence of Potential, Cation Size, and Temperature Lockett, Vera; Sedev, Rossen; Ralston, John The Journal of Physical Chemistry C, Vol. 112, Issue 19 https://doi.org/10.1021/jp7100732	journal	April 2008
The Smallest Amphiphiles: Nanostructure in Protic Room-Temperature Ionic Liquids with Short Alkyl Groups Atkin, Rob; Warr, Gregory G. The Journal of Physical Chemistry B, Vol. 112, Issue 14 https://doi.org/10.1021/jp801190u	journal	April 2008
Density, Refractive Index, Interfacial Tension, and Viscosity of Ionic Liquids [EMIM][EtSO ₄ ], [EMIM][NTf ₂ ], [EMIM][N(CN) ₂ ], and [OMA][NTf ₂ ] in Dependence on Temperature at Atmospheric Pressure Fröba, Andreas P.; Kremer, Heiko; Leipertz, Alfred The Journal of Physical Chemistry B, Vol. 112, Issue 39 https://doi.org/10.1021/jp804319a	journal	October 2008
Ionic Liquids for CO ₂ Capture and Emission Reduction Brennecke, Joan F.; Gurkan, Burcu E. The Journal of Physical Chemistry Letters, Vol. 1, Issue 24 https://doi.org/10.1021/jz1014828	journal	December 2010
Hysteresis of Potential-Dependent Changes in Ion Density and Structure of an Ionic Liquid on a Gold Electrode: In Situ Observation by Surface-Enhanced Infrared Absorption Spectroscopy Motobayashi, Kenta; Minami, Kazuya; Nishi, Naoya The Journal of Physical Chemistry Letters, Vol. 4, Issue 18 https://doi.org/10.1021/jz401645c	journal	September 2013
Structure of [C ₄ mpyr][NTf ₂ ] Room-Temperature Ionic Liquid at Charged Gold Interfaces Lauw, Yansen; Horne, Michael D.; Rodopoulos, Theo Langmuir, Vol. 28, Issue 19 https://doi.org/10.1021/la3005757	journal	May 2012
Materials for electrochemical capacitors Simon, Patrice; Gogotsi, Yury Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2297	journal	November 2008
Ionic-liquid materials for the electrochemical challenges of the future Armand, Michel; Endres, Frank; MacFarlane, Douglas R. Nature Materials, Vol. 8, Issue 8, p. 621-629 https://doi.org/10.1038/nmat2448	journal	July 2009
Can ionic liquids dissolve wood? Processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride Fort, Diego A.; Remsing, Richard C.; Swatloski, Richard P. Green Chemistry, Vol. 9, Issue 1, p. 63-69 https://doi.org/10.1039/B607614A	journal	January 2007
Layering and shear properties of an ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate, confined to nano-films between mica surfaces Perkin, Susan; Albrecht, Tim; Klein, Jacob Phys. Chem. Chem. Phys., Vol. 12, Issue 6 https://doi.org/10.1039/B920571C	journal	January 2010
Recent advances in zinc–air batteries Li, Yanguang; Dai, Hongjie Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00015C	journal	January 2014
Ionic liquid-based electrolytes for “beyond lithium” battery technologies Giffin, Guinevere A. Journal of Materials Chemistry A, Vol. 4, Issue 35 https://doi.org/10.1039/C6TA05260F	journal	January 2016
X-Ray diffraction and resonance shear measurement of nano-confined ionic liquids Tomita, Kazuhito; Mizukami, Masashi; Nakano, Shinya Physical Chemistry Chemical Physics, Vol. 20, Issue 20 https://doi.org/10.1039/C7CP08611C	journal	January 2018
Effects and controls of capacitive hysteresis in ionic liquid electrochemical measurements Lucio, Anthony J.; Shaw, Scott K. The Analyst, Vol. 143, Issue 20 https://doi.org/10.1039/C8AN01085D	journal	January 2018
Potential dependent capacitance of [EMIM][TFSI], [N ₁₁₁₄ ][TFSI] and [PYR ₁₃ ][TFSI] ionic liquids on glassy carbon Klein, Jeffrey M.; Panichi, Evio; Gurkan, Burcu Physical Chemistry Chemical Physics, Vol. 21, Issue 7 https://doi.org/10.1039/C8CP04631J	journal	January 2019
Surface-enhanced Raman scattering Campion, Alan; Kambhampati, Patanjali Chemical Society Reviews, Vol. 27, Issue 4 https://doi.org/10.1039/a827241z	journal	January 1998
Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation Huddleston, Jonathan G.; Visser, Ann E.; Reichert, W. Matthew Green Chemistry, Vol. 3, Issue 4 https://doi.org/10.1039/b103275p	journal	January 2001
A short history of ionic liquids—from molten salts to neoteric solvents Wilkes, John S. Green Chemistry, Vol. 4, Issue 2 https://doi.org/10.1039/b110838g	journal	March 2002
On the concept of ionicity in ionic liquids MacFarlane, Douglas R.; Forsyth, Maria; Izgorodina, Ekaterina I. Physical Chemistry Chemical Physics, Vol. 11, Issue 25 https://doi.org/10.1039/b900201d	journal	January 2009
New insight into the nanostructure of ionic liquids: a small angle X-ray scattering (SAXS) study on liquid tri-alkyl-methyl-ammonium bis(trifluoromethanesulfonyl)amides and their mixtures Pott, Tanja; Méléard, Philippe Physical Chemistry Chemical Physics, Vol. 11, Issue 26 https://doi.org/10.1039/b901582e	journal	January 2009
Differential capacitance of the double layer at the electrode/ionic liquids interface Lockett, Vera; Horne, Mike; Sedev, Rossen Physical Chemistry Chemical Physics, Vol. 12, Issue 39 https://doi.org/10.1039/c0cp00170h	journal	January 2010
The role of the C2 position in interionic interactions of imidazolium based ionic liquids: a vibrational and NMR spectroscopic study Noack, Kristina; Schulz, Peter S.; Paape, Natalia Physical Chemistry Chemical Physics, Vol. 12, Issue 42 https://doi.org/10.1039/c0cp00486c	journal	January 2010
Interfaces of ionic liquids and transition metal surfaces—adsorption, growth, and thermal reactions of ultrathin [C1C1Im][Tf2N] films on metallic and oxidised Ni(111) surfaces Cremer, T.; Wibmer, L.; Calderón, S. Krick Physical Chemistry Chemical Physics, Vol. 14, Issue 15 https://doi.org/10.1039/c2cp40278e	journal	January 2012
Ionic liquid processing of cellulose Wang, Hui; Gurau, Gabriela; Rogers, Robin D. Chemical Society Reviews, Vol. 41, Issue 4 https://doi.org/10.1039/c2cs15311d	journal	January 2012
Tables of molecular vibrational frequencies. Consolidated volume II Shimanouchi, T. Journal of Physical and Chemical Reference Data, Vol. 6, Issue 3 https://doi.org/10.1063/1.555560	journal	July 1977
Double Layer in Ionic Liquids: Overscreening versus Crowding Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A. Physical Review Letters, Vol. 106, Issue 4 https://doi.org/10.1103/PhysRevLett.106.046102	journal	January 2011
CHEMISTRY: Ionic Liquids--Solvents of the Future? Rogers, R. D.; Seddon, Kenneth R. Science, Vol. 302, Issue 5646, p. 792-793 https://doi.org/10.1126/science.1090313	journal	October 2003
Ionic Liquid-Mediated Selective Conversion of CO₂ to CO at Low Overpotentials Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R. Science, Vol. 334, Issue 6056, p. 643-644 https://doi.org/10.1126/science.1209786	journal	September 2011
Structure and Dynamics at Ionic Liquid/Electrode Interfaces Parr, D.; Chrestenson, J.; Malik, K. ECS Transactions, Vol. 66, Issue 30 https://doi.org/10.1149/06630.0035ecst	journal	July 2015
Characterization of the Lithium Surface in N-Methyl-N-alkylpyrrolidinium Bis(trifluoromethanesulfonyl)amide Room-Temperature Ionic Liquid Electrolytes Howlett, P. C.; Brack, N.; Hollenkamp, A. F. Journal of The Electrochemical Society, Vol. 153, Issue 3 https://doi.org/10.1149/1.2164726	journal	January 2006
Ionic liquids. Green solvents for the future Earle, Martyn J.; Seddon, Kenneth R. Pure and Applied Chemistry, Vol. 72, Issue 7 https://doi.org/10.1351/pac200072071391	journal	January 2000
Influence of chloride, water, and organic solvents on the physical properties of ionic liquids Seddon, Kenneth R.; Stark, Annegret; Torres, María-José Pure and Applied Chemistry, Vol. 72, Issue 12 https://doi.org/10.1351/pac200072122275	journal	January 2000

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Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

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