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3-Dimensional atomic scale structure of the ionic liquid–graphite interface elucidated by AM-AFM and quantum chemical simulations

Page, A.J.; Elbourne, A.; Stefanovic, R.; Addicoat, M.A.; Warr, G.G.; Voïtchovsky, K.; Atkin, R.

3-Dimensional atomic scale structure of the ionic liquid–graphite interface elucidated by AM-AFM and quantum chemical simulations Thumbnail


Authors

A.J. Page

A. Elbourne

R. Stefanovic

M.A. Addicoat

G.G. Warr

R. Atkin



Abstract

In situ amplitude modulated atomic force microscopy (AM-AFM) and quantum chemical simulations are used to resolve the structure of the highly ordered pyrolytic graphite (HOPG)–bulk propylammonium nitrate (PAN) interface with resolution comparable with that achieved for frozen ionic liquid (IL) monolayers using STM. This is the first time that (a) molecular resolution images of bulk IL–solid interfaces have been achieved, (b) the lateral structure of the IL graphite interface has been imaged for any IL, (c) AM-AFM has elucidated molecular level structure immersed in a viscous liquid and (d) it has been demonstrated that the IL structure at solid surfaces is a consequence of both thermodynamic and kinetic effects. The lateral structure of the PAN–graphite interface is highly ordered and consists of remarkably well-defined domains of a rhomboidal superstructure composed of propylammonium cations preferentially aligned along two of the three directions in the underlying graphite lattice. The nanostructure is primarily determined by the cation. Van der Waals interactions between the propylammonium chains and the surface mean that the cation is enriched in the surface layer, and is much less mobile than the anion. The presence of a heterogeneous lateral structure at an ionic liquid–solid interface has wide ranging ramifications for ionic liquid applications, including lubrication, capacitive charge storage and electrodeposition.

Citation

Page, A., Elbourne, A., Stefanovic, R., Addicoat, M., Warr, G., Voïtchovsky, K., & Atkin, R. (2014). 3-Dimensional atomic scale structure of the ionic liquid–graphite interface elucidated by AM-AFM and quantum chemical simulations. Nanoscale, 6(14), 8100-8106. https://doi.org/10.1039/c4nr01219d

Journal Article Type Article
Publication Date Jul 27, 2014
Deposit Date Aug 15, 2014
Publicly Available Date Mar 28, 2024
Journal Nanoscale
Print ISSN 2040-3364
Electronic ISSN 2040-3372
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 6
Issue 14
Pages 8100-8106
DOI https://doi.org/10.1039/c4nr01219d

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