Electron Transfer Kinetics on Mono- and Multi-Layer Graphene

Since the first isolation of graphene monolayer via mechanical exfoliation in 2004, many other production methods have emerged in the following years. These methods include chemical vapour deposition, liquid phase graphite exfoliation, graphite oxide reduction and epitaxial growth, each having its pros and cons. The unique properties of graphene, such as high electron mobility, large specific surface area, mechanical strength and high transparency, ignited an enormous research interest to explore the electrochemical properties of graphene sheets, with potential uses in many immediate applications such as energy storage, solar cell technology and corrosion protection. Understanding how the electron transfer kinetics of a redox reaction between the graphene surface and a molecule compares to graphite or other carbon based materials is crucial to future use of graphene as a ‘supreme’ electrode material.¹

Herein, the electrochemical response of mono-layer and multi-layer graphene electrodes, prepared using both chemical vapour deposition and mechanical exfoliation, is presented. Experiments were carried out using a microinjector, micromanipulator and optical microscopy, enabling precise deposition of size-controlled droplets on the flake surface.¹ The insulating substrates used for flake preparation include inorganic materials and organic polymers. Graphene/graphite flakes were characterised using optical microscopy, Raman spectroscopy and atomic force microscopy.

The electron transfer rate at the basal planes, edge planes and boundaries between graphene flakes was determined using voltammetric techniques. The redox couple, number of graphene layers, presence of defects and nature of the substrate are all shown to have a significant effect on the electrochemical activity.^2-3 Furthermore, the stability of the droplets on the surface depends on various factors, such as the solvent choice, electrolyte content, number of graphene layers, underlying substrate and method of flake preparation.

1.   Valota, A. T.; Toth, P. S.; Kim, Y. J.; Hong, B. H.; Kinloch, I. A.; Novoselov, K. S.; Hill, E. W.; Dryfe, R. A. W., Electrochimica Acta, 2013, 110, 9-15.

2.   Valota, A. T.; Kinloch, I. A.; Novoselov, K. S.; Casiraghi, C.; Eckmann, A.; Hill, E. W.; Dryfe, R. A. W., ACS Nano, 2011, 5 (11), 8809-8815.

3.   P. S. Toth; A. Valota; M. Velicky; I. Kinloch; K. Novoselov; E. W. Hill; R. A. W. Dryfe, Chemical Science, 2013, DOI:10.1039/C3SC52026A.