Electron transfer kinetics on natural crystals of MoS2 and graphite

Matej Velicky, Mark A. Bissett, Peter S. Toth, Hollie V. Patten, Stephen D. Worrall, Andrew N J Rodgers, Ernie W. Hill, Ian A. Kinloch, Konstantin S. Novoselov, Thanasis Georgiou, Liam Britnell, Robert A W Dryfe

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Abstract

Here, we evaluate the electrochemical performance of sparsely studied natural crystals of molybdenite and graphite, which have increasingly been used for fabrication of next generation monolayer molybdenum disulphide and graphene energy storage devices. Heterogeneous electron transfer kinetics of several redox mediators, including Fe(CN)63-/4-, Ru(NH3)63+/2+ and IrCl62-/3- are determined using voltammetry in a micro-droplet cell. The kinetics on both materials are studied as a function of surface defectiveness, surface ageing, applied potential and illumination. We find that the basal planes of both natural MoS2 and graphite show significant electroactivity, but a large decrease in electron transfer kinetics is observed on atmosphere-aged surfaces in comparison to in situ freshly cleaved surfaces of both materials. This is attributed to surface oxidation and adsorption of airborne contaminants at the surface exposed to an ambient environment. In contrast to semimetallic graphite, the electrode kinetics on semiconducting MoS2 are strongly dependent on the surface illumination and applied potential. Furthermore, while visibly present defects/cracks do not significantly affect the response of graphite, the kinetics on MoS2 systematically accelerate with small increase in disorder. These findings have direct implications for use of MoS2 and graphene/graphite as electrode materials in electrochemistry-related applications.

Original languageEnglish
Pages (from-to)17844-17853
Number of pages10
Journal Physical Chemistry Chemical Physics
Volume17
Issue number27
Early online date12 Jun 2015
DOIs
Publication statusPublished - 2015

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Velicky, M., Bissett, M. A., Toth, P. S., Patten, H. V., Worrall, S. D., Rodgers, A. N. J., ... Dryfe, R. A. W. (2015). Electron transfer kinetics on natural crystals of MoS2 and graphite. Physical Chemistry Chemical Physics , 17(27), 17844-17853. https://doi.org/10.1039/c5cp02490k