The mechanisms of pyrrole electropolymerization

Over the past twenty years, polypyrrole has appeared as the most extensively studied conducting polymer. However, despite the volume of work already done in this area, there has been little focus put on the mechanism of polypyrrole synthesis, especially concerning the most efficient method, electropolymerization. Numerous analytical techniques have been used to study polypyrrole electrodeposition and/or doping. However, the mechanism itself is still a controversial subject as there is not one mechanism which is universally accepted. The mechanism proposed by Diaz is the one most commonly referred to in the literature although several other mechanisms are not lacking in support. The controversy lies in the initiation step as each mechanism proposes a different way of beginning the reaction, varying between electron transfer, proton transfer and direct radical pyrrole formation. Without considering the initiation step, there are many other factors including electrolyte, solvent, temperature and pH which can influence the reaction mechanism during the electropolymerization of pyrrole, thus impacting the characteristics of the polymer formed at the electrode.