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Hofmeister effects influence bulk nanostructure in a protic ionic liquid.

Thomas Bourke1, Kasimir P Gregory2, Alister J Page1

  • 1Discipline of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia.

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|May 8, 2023
PubMed
Summary
This summary is machine-generated.

Specific ion effects influence hydrogen bonding in nanostructured ionic liquids. Dissolved cations strengthen hydrogen bonds, while anions show ion-specific effects, with fluoride disrupting and iodide promoting interactions in propylammonium nitrate (PAN).

Keywords:
Hofmeister effectHydrogen bondIonic liquidNanostructureSpecific ion effect

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Specific ion effects are well-studied in water and molecular solvents but poorly understood in complex systems like ionic liquids.
  • Nanostructured ionic liquids, such as propylammonium nitrate (PAN), possess unique hydrogen bonding networks.
  • Investigating ion-specific impacts on these networks is crucial for understanding and manipulating ionic liquid properties.

Purpose of the Study:

  • To investigate the influence of dissolved monovalent salts on the nanostructure and hydrogen bonding of propylammonium nitrate (PAN).
  • To determine if the observed effects constitute specific ion effects, dependent on ion identity.
  • To assess the applicability of existing specific ion effect predictors to complex ionic liquid systems.

Main Methods:

  • Molecular dynamics simulations were employed to model bulk PAN and solutions containing varying concentrations of PAN with different halide anions (F-, Cl-, Br-, I-) and alkali metal cations (Li+, Na+, K+, Rb+).
  • Analysis focused on the hydrogen bond network within the polar and non-polar domains of the PAN nanostructure.
  • A recently proposed predictor of specific ion effects was utilized to rationalize the simulation results.

Main Results:

  • Propylammonium nitrate (PAN) exhibits a distinct hydrogen bond network within its nanostructure.
  • Dissolved alkali metal cations consistently enhanced hydrogen bonding in the PAN polar domain.
  • Halide anions demonstrated ion-specific effects: fluoride (F-) disrupted hydrogen bonding, while iodide (I-) promoted it.
  • These ion-dependent modulations of hydrogen bonding confirm the presence of specific ion effects in PAN.

Conclusions:

  • The study confirms that specific ion effects significantly influence hydrogen bonding in the nanostructured ionic liquid propylammonium nitrate (PAN).
  • The identity of both cations and anions dictates their impact on the hydrogen bond network.
  • Existing theoretical frameworks for predicting specific ion effects can be extended to complex ionic liquid environments.