Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers

Herein we demonstrate that ionic liquids can form long-lived double layers, generating electric fields detectable by straightforward open circuit potential (OCP) measurements. In imidazolium-based ionic liquids an external negative voltage pulse leads to an exceedingly stable near-surface dipolar la...

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Main Authors: Belotti, Mattia, Lyu, Xin, Xu, L., Halat, P., Darwish, Nadim, Silvester-Dean, Debbie, Goh, Ching, Izgorodina, E.I., Coote, M.L., Ciampi, Simone
Format: Journal Article
Language:English
Published: AMER CHEMICAL SOC 2021
Subjects:
Online Access:http://purl.org/au-research/grants/arc/DP190100735
http://hdl.handle.net/20.500.11937/90479
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author Belotti, Mattia
Lyu, Xin
Xu, L.
Halat, P.
Darwish, Nadim
Silvester-Dean, Debbie
Goh, Ching
Izgorodina, E.I.
Coote, M.L.
Ciampi, Simone
author_facet Belotti, Mattia
Lyu, Xin
Xu, L.
Halat, P.
Darwish, Nadim
Silvester-Dean, Debbie
Goh, Ching
Izgorodina, E.I.
Coote, M.L.
Ciampi, Simone
author_sort Belotti, Mattia
building Curtin Institutional Repository
collection Online Access
description Herein we demonstrate that ionic liquids can form long-lived double layers, generating electric fields detectable by straightforward open circuit potential (OCP) measurements. In imidazolium-based ionic liquids an external negative voltage pulse leads to an exceedingly stable near-surface dipolar layer, whose field manifests as long-lived (∼1-100 h) discrete plateaus in OCP versus time traces. These plateaus occur within an ionic liquid-specific and sharp potential window, defining a simple experimental method to probe the onset of interfacial ordering phenomena, such as overscreening and crowding. Molecular dynamics modeling reveals that the OCP arises from the alignment of the individual ion dipoles to the external electric field pulse, with the magnitude of the resulting OCP correlating with the product of the projected dipole moment of the cation and the ratio between the cation diffusion coefficient and its volume. Our findings also reveal that a stable overscreened structure is more likely to form if the interface is first forced through crowding, possibly accounting for the scattered literature data on relaxation kinetics of near-surface structures in ionic liquids.
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spelling curtin-20.500.11937-904792023-03-20T02:07:17Z Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers Belotti, Mattia Lyu, Xin Xu, L. Halat, P. Darwish, Nadim Silvester-Dean, Debbie Goh, Ching Izgorodina, E.I. Coote, M.L. Ciampi, Simone Science & Technology Physical Sciences Chemistry, Multidisciplinary Chemistry FREQUENCY GENERATION SPECTROSCOPY DOUBLE-LAYER DIFFERENTIAL CAPACITANCE ELECTROSTATIC CATALYSIS FREE ANALYZER INTERFACE ELECTROLYTE COEFFICIENTS RELAXATION MONOLAYERS Herein we demonstrate that ionic liquids can form long-lived double layers, generating electric fields detectable by straightforward open circuit potential (OCP) measurements. In imidazolium-based ionic liquids an external negative voltage pulse leads to an exceedingly stable near-surface dipolar layer, whose field manifests as long-lived (∼1-100 h) discrete plateaus in OCP versus time traces. These plateaus occur within an ionic liquid-specific and sharp potential window, defining a simple experimental method to probe the onset of interfacial ordering phenomena, such as overscreening and crowding. Molecular dynamics modeling reveals that the OCP arises from the alignment of the individual ion dipoles to the external electric field pulse, with the magnitude of the resulting OCP correlating with the product of the projected dipole moment of the cation and the ratio between the cation diffusion coefficient and its volume. Our findings also reveal that a stable overscreened structure is more likely to form if the interface is first forced through crowding, possibly accounting for the scattered literature data on relaxation kinetics of near-surface structures in ionic liquids. 2021 Journal Article http://hdl.handle.net/20.500.11937/90479 10.1021/jacs.1c06385 English http://purl.org/au-research/grants/arc/DP190100735 http://purl.org/au-research/grants/arc/FT190100148 http://purl.org/au-research/grants/arc/FL170100041 AMER CHEMICAL SOC fulltext
spellingShingle Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
FREQUENCY GENERATION SPECTROSCOPY
DOUBLE-LAYER
DIFFERENTIAL CAPACITANCE
ELECTROSTATIC CATALYSIS
FREE ANALYZER
INTERFACE
ELECTROLYTE
COEFFICIENTS
RELAXATION
MONOLAYERS
Belotti, Mattia
Lyu, Xin
Xu, L.
Halat, P.
Darwish, Nadim
Silvester-Dean, Debbie
Goh, Ching
Izgorodina, E.I.
Coote, M.L.
Ciampi, Simone
Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title_full Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title_fullStr Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title_full_unstemmed Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title_short Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers
title_sort experimental evidence of long-lived electric fields of ionic liquid bilayers
topic Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
FREQUENCY GENERATION SPECTROSCOPY
DOUBLE-LAYER
DIFFERENTIAL CAPACITANCE
ELECTROSTATIC CATALYSIS
FREE ANALYZER
INTERFACE
ELECTROLYTE
COEFFICIENTS
RELAXATION
MONOLAYERS
url http://purl.org/au-research/grants/arc/DP190100735
http://purl.org/au-research/grants/arc/DP190100735
http://purl.org/au-research/grants/arc/DP190100735
http://hdl.handle.net/20.500.11937/90479