Polymer films on electrodes: Part III. Digital simulation model for cyclic voltammetry of electroactive polymer film and electrochemistry of poly(vinylferrocene) on platinum

The electrochemistry of electrodeposited poly(vinylferrocene) (PVF) and poly(vinylferrocene acrylonitrile) (PVFAN) films on platinum electrodes was studied in acetonitrile solutions using perchlorate or p-toluenesulfonate as the counter ion by cyclic voltammetry. A model is proposed for the cyclic voltammetric behavior of polymeric films on electrode surfaces. The model incorporates non-equivalent redox sites with interconversion between such sites, electron-transfer kinetics at substrate/film interface and diffusion within the film. Parameters are obtained which yield a good fit to the experimental results.