Screening of ion–graphene electrode interactions by ionic liquids: the effects of liquid structure

Vladislav V. Ivaništšev, Maxim V. M.V. Fedorov, Ruth M. R.M. Lynden-Bell

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

We have investigated the screening of solute ion–electrode interactions in two ionic liquids (1-butyl 3-methylimidazolium tetrafluoroborate [BMIm][BF4] and 1,3-dimethylimidazolium chloride [MMIm]Cl) by constructing free energy profiles for dissolved charged probes as a function of distance from a charged surface (graphene). The free energy profiles for three types of mutual interactions (surface and solute with opposite charges, solute and uncharged surface, and surface and solute with the same charges) differ from each other, but are remarkably similar in the two ionic liquids. They all show oscillations rather than the monotonic behavior predicted by Debye-type screening models. In both ionic liquids, there are high barriers impeding the motion of charged probes to the oppositely charged surface. We examined the local liquid structure around the probes and found that the free energy minima correspond to positions in which the solvation layers induced by the surface charge and the solvation shells around the probes enhance each other while barriers occur where they perturb each other.
LanguageEnglish
Pages5841-5847
Number of pages7
JournalJournal of Physical Chemistry C
Volume118
Issue number11
Early online date16 Feb 2014
DOIs
Publication statusPublished - 20 Mar 2014

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Ionic Liquids
Graphite
Ionic liquids
Graphene
Screening
graphene
screening
Ions
solutes
Electrodes
electrodes
Free energy
Liquids
liquids
probes
free energy
Solvation
ions
interactions
solvation

Keywords

  • ion-graphene electrode interactions
  • ionic liquids
  • screening
  • effects
  • liquid structure

Cite this

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abstract = "We have investigated the screening of solute ion–electrode interactions in two ionic liquids (1-butyl 3-methylimidazolium tetrafluoroborate [BMIm][BF4] and 1,3-dimethylimidazolium chloride [MMIm]Cl) by constructing free energy profiles for dissolved charged probes as a function of distance from a charged surface (graphene). The free energy profiles for three types of mutual interactions (surface and solute with opposite charges, solute and uncharged surface, and surface and solute with the same charges) differ from each other, but are remarkably similar in the two ionic liquids. They all show oscillations rather than the monotonic behavior predicted by Debye-type screening models. In both ionic liquids, there are high barriers impeding the motion of charged probes to the oppositely charged surface. We examined the local liquid structure around the probes and found that the free energy minima correspond to positions in which the solvation layers induced by the surface charge and the solvation shells around the probes enhance each other while barriers occur where they perturb each other.",
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Screening of ion–graphene electrode interactions by ionic liquids : the effects of liquid structure. / Ivaništšev, Vladislav V.; Fedorov, Maxim V. M.V.; Lynden-Bell, Ruth M. R.M.

In: Journal of Physical Chemistry C, Vol. 118, No. 11, 20.03.2014, p. 5841-5847.

Research output: Contribution to journalArticle

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