Cyclic voltammetry on electrode surfaces covered with porous layers: An analysis of electron transfer kinetics at single-walled carbon nanotube modified electrodes

Cyclic voltammetry is recorded of the oxidation of ferrocyanide on a glassy carbon electrode modified with multiple layers of single-walled carbon nanotubes. The current response is interpreted in terms of semi-infinite planar diffusion towards the macro-electrode surface and in terms of oxidation of the electroactive species trapped in pockets in between the nanotubes. A thin layer model is used to illustrate the effects of diffusion within a porous layer. It is found that a semi-infinite planar diffusion model alone is not appropriate for interpreting the kinetics of the electron transfer at this electrode surface. In particular, caution should be exercised in respect of comparing voltammetric peak-to-peak potential separations between naked electrodes and nanotube-modified electrodes for the inference of electrocatalysis via electron transfer via the nanotubes.