Electrochemical measurements of the ion conductivity, permselectivity and transference numbers of polypyrrole and polypyrrole derivatives

Abstract

Electrochemical dc and ac measurements were carried out on free-standing polypyrrole (ppy) membranes to study the ion conductivity and permselectivity of the polymer as a function of the oxidation state. The membranes were prepared by electropolymerisation and mounted in a two-compartment cell, where the oxidation state of the ppy membrane could be adjusted by potentiostatic polarisation and the ion conductivity and permselectivity of the polymer could be measured in a symmetrical electrolyte/membrane/electrolyte configuration. Combining constant current permeation experiments with solution analysis using ion chromatography (IC) and atomic absorption spectroscopy (AAS), it was demonstrated that ppy exhibits not only an appreciable ion conductivity but also a distinct permeability and selectivity for anions in the oxidised state. Incorporation of immobile anions like dodecylsulfate or copolymerization with a modified pyrrole monomer like N-sulfopropyl-pyrrole carrying a sulfonate group leads to modified membranes which exhibit distinct cation permselectivity in the reduced state. Such a membrane can be switched dynamically between anion and cation permeability through electrochemical oxidation and reduction of the polymer backbone.