Ionic Motion in Polypyrrole−Cellulose Composites: Trap Release Mechanism during Potentiostatic Reduction

Abstract

This work investigates the movement of anions during potentiostatic controlled reduction of novel composite materials consisting of high surface area cellulose substrates, extracted from the Cladophora sp. algae, coated with thin ( approximately 50 nm) layers of the intrinsically conducting polymer (ICP) polypyrrole. The coating was achieved by chemical polymerization of pyrrole on the cellulose fibers with iron(III) chloride and phosphomolybdic acid, respectively. The composites are in the form of paper sheets and can be directly immersed into an electrolyte solution for ion absorption/desorption. The motion of glutamate and aspartate anions during cathodic polarization was investigated as a function of preceding anodic polarization at various potentials. The composite was found to exhibit memory effect as the response to a cathodic polarization of constant magnitude produced different responses depending on the magnitude of the preceding anodic potential. After the application of a cathodic potential to the composite, the reduction current curvesgenerated by anions leaving the compositewere found to initially increase in magnitude followed by a monotonic decay. A similar response has not been described and analyzed for electrochemical reduction of anion containing ICP materials earlier. A theoretical model was developed to aid the analysis of the experimental data. The model accounts for both freely mobile anions and anions that may be temporarily trapped in a contracting PPy network during cathodic polarization. By fitting the recorded reduction current curves to this model, detailed information about the ionic movement in the composite could be obtained, which may be used to further optimize the materials properties of conducting polymer systems aimed for specific electrochemical ion exchange processes.