Mechanism of ionic and redox sensitivity of p-type conducting polymers

Abstract The potentiometric response of polypyrrole films is studied. The films are electrochemically deposited on platinum. The effects of film thickness, counter-anions and film conditioning on the response are studied. It is demonstrated that the response can vary from anionic to cationic, depending on the charge-compensating counter-anion (doping anion) incorporated during electropolymerization. Furthermore, the ionic response may be altered by redox couples in the solution, and under some conditions polypyrrole may also act as a pure redox electrode. The mixed ionic and redox sensitivities of polypyrrole are explained by considering both ion and electron transfer at the polymer | solution interface. The experimental results are related to a theoretical model developed for p-type conducting polymers

[1]  C. Santamaría,et al.  Kinetics of the polypyrrole electrogeneration from aqueous solution. An ex situ microgravimetric study , 1992 .

[2]  M. Sato.  Half-cell potentials of semiconductive simple binary sulphides in aqueous solution , 1966 .

[3]  Q. Pei,et al.  Electrode potentials of electronically conducting polymer polypyrrole , 1992 .

[4]  G. Tourillon,et al.  Stability of Conducting Polythiophene and Derivatives , 1983 .

[5]  M. Koebel.  Standard potentials of solid-state metal ion-selective electrodes , 1974 .

[6]  A. Lewenstam,et al.  Diffusion-layer model for copper solid-state chalcocite membrane electrode; sensitivity to copper(II) ions. , 1976, Talanta.

[7]  R. Buck,et al.  Comparison of proposed response mechanisms of precipitate-based ion-selective electrodes in the presence of interfering ions , 1989 .

[8]  R. Buck,et al.  Reversible metal/salt interfaces and the relation of second kind and all-solid-state membrane electrodes , 1974 .

[9]  Dermot Diamond,et al.  All-solid-state sodium-selective electrode based on a calixarene ionophore in a poly(vinyl chloride) membrane with a polypyrrole solid contact , 1992 .

[10]  E. Pungor,et al.  Kriterien für die Eignung einer chemischen Verbindung als Indikatorelektrodenmaterial bei potentiometrischen Verfahren auf der Grundlage von einfachen Redoxsystemen , 1969 .

[11]  A. Lewenstam,et al.  Model for treatment of selectivity coefficients for solid-state ion-selective electrodes , 1981 .

[12]  R. Buck,et al.  Influence of Contact Materials on Electric Properties of Single Crystal AgBr , 1989 .

[13]  G. Horvai,et al.  Donnan exclusion failure in low anion site density membranes containing valinomycin , 1987 .

[14]  Shaojun Dong,et al.  Chloride chemical sensor based on an organic conducting polypyrrole polymer , 1988 .

[15]  F. B. Diniz,et al.  Aspects of electron transfer at a conducting membrane-solution interface , 1989 .

[16]  S. Trasatti,et al.  The solubility of metals in liquid polar phases , 1977 .

[17]  A. Ivaska,et al.  Anionic responses of electrochemically synthesized polypyrrole films. , 1992, Talanta.

[18]  H. Hayashi,et al.  Polymer-based cation-selective electrodes modified with naphthalenesulphonates , 1991 .

[19]  K. Doblhofer.  The non-metallic character of solvated conducting polymers , 1992 .

[20]  A. Lewenstam,et al.  Response mechanism of solid-state ion-selective electrodes in the presence of interfering ions , 1987 .

[21]  W. E. Morf.  Time-dependent selectivity behavior and dynamic response of silver halide membrane electrodes to interfering ions , 1983 .

[22]  P. Wrona.  On the interpretation of the electrode potential , 1979 .

[23]  S. Bruckenstein,et al.  Solvent and salt transfer upon redox switching of electroactive polymers , 1991 .

[24]  G. Wallace,et al.  The use of electropolymerization to produce new sensing surfaces: A review emphasizing electrode position of heteroaromatic compounds , 1991 .

[25]  A. Frumkin,et al.  Real free solvation energy of an electron in a solution in equilibrium with the electrode and its dependence on the solvent nature , 1977 .

[26]  S. Dong,et al.  STUDY OF CIO4-SELECTIVE ELECTRODE BASED ON A CONDUCTING POLYMER POLYPYRROLE , 1989 .

[27]  D. Pletcher,et al.  The electrodeposition of polypyrrole films from aqueous solutions , 1984 .

[28]  C. Zhong,et al.  Polypyrrole-based electrode coatings switchable electrochemically between the anion- and cation-exchanger states , 1990 .

[29]  A. Ivaska,et al.  Study of polypyrrole film as redox electrode , 1993 .

[30]  P. Vanýsek,et al.  Interfacial potential differences at mixed conductor interfaces : Nernst, Nernst-Donnan, Nernst distribution and generalizations , 1990 .

[31]  P. Christensen,et al.  IN SITU SPECTROSCOPIC INVESTIGATIONS OF THE GROWTH, ELECTROCHEMICAL CYCLING AND OVEROXIDATION OF POLYPYRROLE IN AQUEOUS SOLUTION , 1991 .

[32]  A. Ivaska.  Analytical applications of conducting polymers , 1991 .

[33]  G. Bidan,et al.  Conductive polymers with immobilised dopants: ionomer composites and auto-doped polymers-a review and recent advances , 1988 .

[34]  T. Amemiya,et al.  Analyses of Spectroelectrochemical Behavior of Polypyrrole Films Using the Nernst Equation “Monomer Unit Model” and Polaron/Bipolaron Model , 1991 .