Electrochemical Investigation of Adsorption of Single-Wall Carbon Nanotubes at a Liquid/Liquid Interface.

There is much interest in understanding the interfacial properties of carbon nanotubes, particularly at water/oil interfaces. Here, the adsorption of single-wall carbon nanotubes (SWCNTs) at the water/1,2-dichloroethane (DCE) interface, and the subsequent investigation of the influence of the adsorbed nanotube layer on interfacial ion transfer, is studied by using the voltammetric transfer of tetramethylammonium (TMA+) and hexafluorophosphate (PF6-) as probe ions. The presence of the interfacial SWCNT layer significantly suppresses the transfer of both ions across the interface, with a greater degree of selectivity towards the PF6- ion. This effect was attributed both to the partial blocking of the interface by the SWCNTs and to the potential dependant adsorption of background electrolyte ions on the surface of the SWCNTs, as confirmed by X-ray photoelectron spectroscopy, which is caused by an electrostatic interaction between the interfacial SWCNTs and the transferring ion.

Electrostatic Stabilization of Graphene in Organic Dispersions.

The exfoliation of graphite to give graphene dispersions in nonaqueous solvents is an important area with regards to scalable production of graphene in bulk quantities and its ultimate application in devices. Understanding the mechanisms governing the stability of these dispersions is therefore of both scientific interest and technological importance. Herein, we have used addition of an indifferent electrolyte to perturb few-layer graphene dispersions in a nonaqueous solvent (1,2-dichloroethane) as a way to probe the importance of interparticle electrostatic repulsions toward the overall dispersion stability. At a sufficient electrolyte concentration, complete sedimentation of the dispersions occurred over 24 h, and the relationship between dispersed graphene concentration and electrolyte concentration was consistent with a dispersion stabilized by electrostatic repulsions. We also found that an increased oxygen content in the graphite starting material produced dispersions of greater stability, indicating that the extent of oxidation is an important parameter in determining the extent of electrostatic stabilization in nonaqueous graphene dispersions.

Electron transfer kinetics on natural crystals of MoS2 and graphite.

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)6(3-/4-), Ru(NH3)6(3+/2+) and IrCl6(2-/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.