Issue 11, 2014

The ionic liquid–vacuum outer atomic surface: a low-energy ion scattering study

Abstract

We have identified elements present in the ionic liquid–vacuum outer atomic surface of 23 ionic liquids using high sensitivity low-energy ion scattering (LEIS), a very surface sensitive technique. We show that the probability of cationic heteroatoms being present at the ionic liquid–vacuum outer atomic surface is very low; we detected imidazolium nitrogen for only one of the 18 imidazolium based ionic liquids investigated, no nitrogen for the two ammonium based ionic liquids and a very small amount of phosphorus for two of the three phosphonium-based ionic liquids. We determine that the anion is always present at the ionic liquid–vacuum outer atomic surface, even for very large cations containing dodecyl alkyl chains or longer; these chains dominate the ionic liquid–vacuum outer atomic surface, but are not sufficiently densely packed to completely cover the anions. We demonstrate the presence of strong hydrogen bond acceptor adsorption sites at the ionic liquid–vacuum outer atomic surface. We demonstrate that the amount of ion present at the ionic liquid–vacuum outer atomic surface can be tuned by varying the size of the other ion; larger cations (or anions) occupy more of the ionic liquid–vacuum outer atomic surface, leaving less room for anions (or cations). By identifying elements present at the ionic liquid–vacuum outer atomic surface, conclusions can be drawn on the orientations of anions nearest the vacuum. We show that for five different anions there is a most probable ion orientation, but other anion orientations also exist, demonstrating the presence of multiple anion orientations. The imidazolium cations nearest to the vacuum also show similar multi-orientation behaviour. This variety of atoms present and therefore ion orientations is expected to be central to controlling surface reactivity. In addition, our results can be used to quantitatively validate simulations of the ionic liquid–vacuum surface at a molecular level. Overall, our studies, in combination with literature data from different techniques and simulations, provide a clear picture of ionic liquid–vacuum outer atomic surfaces.

Graphical abstract: The ionic liquid–vacuum outer atomic surface: a low-energy ion scattering study

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Feb 2014
Accepted
07 Jul 2014
First published
08 Jul 2014
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2014,5, 4404-4418

Author version available

The ionic liquid–vacuum outer atomic surface: a low-energy ion scattering study

I. J. Villar-Garcia, S. Fearn, G. F. De Gregorio, N. L. Ismail, F. J. V. Gschwend, A. J. S. McIntosh and K. R. J. Lovelock, Chem. Sci., 2014, 5, 4404 DOI: 10.1039/C4SC00640B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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