The Metal/Electroactive Polymer Interface Studied by Surface Resistance


The experimental arrangement in this investigation was one in which a poly(o-aminophenol) (POAP) film was supported on a thin gold film electrode whose thickness is of the order of the mean free path of conduction electrons of gold. This arrangement allows one to apply the surface resistance technique to study the electrochemical processes occurring at the metal film surface coated with the polymer film. The dependence of the resistance change of the thin gold film electrode on the external electrolyte composition for polymer thickness lower than 0.25, was attributed to a competition, at the gold film surface, between the redox process of the polymer and adsorption of different ion species contained in the electrolyte. This competition reflects a discontinuous character of polymer thickness lower than 0.25 at the metal polymer interface. The resistance response of the metal film becomes independent of both the external electrolyte composition and polymer thickness for polymer thickness higher than 0.8 Then, POAP thicknesses higher than 0.8 seem to be compact enough at the metal polymer interface to prevent the interaction of the species contained in the supporting electrolyte with the gold film surface. The increase of the gold film resistance in going from the reduced to the oxidized state for POAP thicknesses higher than 0.8 was attributed to the redox conversion of poly(o-aminophenol) from amine to imine groups. This resistance increase was explained as a transition from specular to diffuse scattering of conduction electrons of gold at the gold poly(o-aminophenol) interface due to a less compact distribution of oxidised sites of POAP as compared with that of the reduced ones. An attenuation of the resistance response of the gold film was observed when the POAP films were deactivated either by contact with a ferric cation solution or prolonged potential cycling. The deactivation of the polymer film was attributed to the creation of inactive gaps within the redox sites configuration of POAP. The surface resistance technique allows one to detect different redox sites configurations of POAP on the gold film, according to the method used to deactivate the polymer films. In this work, it is demonstrated that the surface resistance technique can be employed to study not only the ability of a POAP film to inhibit the interaction of different species in solution with a metal surface but also the deactivation of the polymer film.

Share and Cite:

Tucceri, R. (2013) The Metal/Electroactive Polymer Interface Studied by Surface Resistance. Journal of Surface Engineered Materials and Advanced Technology, 3, 205-216. doi: 10.4236/jsemat.2013.33028.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] J. W. Geus, “Chemisorption and Reaction on Metallic Films,” In: J. R. Anderson and G. Hohler, Eds., Vol. 1, Academic Press, London, 1971, p. 388,
[2] D. Schumacher, “Surface Scattering Experiments with Conduction Electrons,” In: J. R. Anderson and G. Hohler, Eds., Vol. 128, Springer Tracts in Modern Physics, Springer, Berlin, 1992, p. 67
[3] R. Tucceri, “A Review about the Surface Resistance Technique in Electrochemistry,” Surface Science Reports, Vol. 56, No. 3-4, 2004, pp. 85-157. doi:10.1016/j.surfrep.2004.09.001
[4] R. I. Tucceri and D. Posadas, “Surface Conductance Study of the Anion Adsorption on Gold,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 191, No. 2, 1985, pp. 387-399. doi:10.1016/S0022-0728(85)80031-0
[5] F. M. Romeo, R. I. Tucceri and D. Posadas, “Surface Conductivity Changes during the Electrochemical Adsorption of UPD Layers on Silver and Gold,” Surface Science, Vol. 203, No. 1-2, 1988, pp. 186-200. doi:10.1016/0039-6028(88)90203-8
[6] R. I. Tucceri and D. Posadas, “Resistive Behavior of Thin Gold Film Electrodes under Direct Current Polarization,” Journal of the Electrochemical Society, Vol. 130, No. 1, 1983, pp. 104-107. doi:10.1149/1.2119631
[7] R. I. Tucceri and D. Posadas, “Theoretical Approach to the Resistive Behavior of Thin Solid Film Electrode under Direct Current Polarization,” Journal of the Electrochemical SocietyVol. 128, No. 7, 1981, pp. 1478-1483. doi:10.1149/1.2127667
[8] C. Barbero, J. J. Silber and L. Sereno, “Formation of a Novel Electroactive Film by Electropolynerization or Orthoaminophenol, Study of Its Electrochemical Structure and Formation Mechanism. Electropolymerization of Analogous Compounds,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 263, No. 2, 1989, pp. 333-352. doi:10.1016/0022-0728(89)85103-4
[9] C. Barbero, J. J. Silber and L. Sereno, “Electrochemical Properties of Poly(o-Aminophenol) Modified Electrodes in Aqueous Acid Solutions,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 291, No. 1-2, 1990, pp. 81-101. doi:10.1016/0022-0728(90)87179-N
[10] C. Barbero, J. Zerbino, L. Sereno and D. Posadas, “Optical Properties of Electropolymerized Orthoaminophenol,” Electrochimica Acta, Vol. 32, No. 4, 1987, pp. 693-697. doi:10.1016/0013-4686(87)87063-9
[11] S. Kunimura, T. Ohsaka and N. Oyama, “ Preparation of Thin Polymeric Films on Electrode Surfaces by Electropolymerization of Orthoaminophenol,” Macromolecules, Vol. 21, No. 4, 1988, pp. 894-900. doi:10.1021/ma00182a007
[12] R. I. Tucceri, C. Barbero, J. J. Silber, L. Sereno and D. Posadas, “Spectroelectrochemical Study of Poly-o-Aminophenol,” Electrochimica Acta, Vol. 42, No. 6, 1997, pp. 919-927. doi:10.1016/S0013-4686(96)00277-0
[13] C. Barbero, R. I. Tucceri, D. Posadas, J. J. Silber and L. Sereno, “Impedance Characteristics of Poly-o-Aminophenol Electrodes,” Electrochimica Acta, Vol. 40, No. 8, 1995, pp. 1037-1040. doi:10.1016/0013-4686(94)00373-9
[14] F. J. Rodríguez Nieto and R. I. Tucceri, “The pH Effect on the Charge Transport at Redox Polymer-Modified Electrodes. An AC Impedance Study Applied to Poly(o-Aminophenol) film Electrodes,” Journal of Electroanalytical Chemistry, Vol. 416, No. 1-2, 1996, pp. 1-24. doi:10.1016/S0022-0728(96)04704-3
[15] A. Bonfranceschi, A. Pérez Córdoba, S. Keunchkarian, S. Zapata and R. Tucceri, “Transport Acorss Poly(o-Aminophenol) Modified Electrodes in Contact with Media Containing Redox Active Couples. A study Using Rotating Disc Electrode Voltammetry,” Journal of Electroanalytical Chemistry, Vol. 477, No. 1, 1999, pp. 1-13. doi:10.1016/S0022-0728(99)00368-X
[16] R. I. Tucceri, “Redox Mediation and Permeation Process at Deactivated Poly(o-Aminophenol) Films. A Study Applying Rotating Disc Electrode Voltammetry and Electrochemical Impedance Spectroscopy,” Journal of Electroanalytical Chemistry, Vol. 633, No. 1, 2009, pp. 198-206. doi:10.1016/j.jelechem.2009.05.014
[17] R. Tucceri, “Charge Transfer and Charge Transport Parameters at Deactivated Poly(o-Aminophenol) Film Electrodes. A Study Applying Electrochemical Impedance Spectroscopy,” Journal of Electroanalytical Chemistry, Vol. 659, No. 1, 2011, pp. 83-91. doi:10.1016/j.jelechem.2011.05.005
[18] J. Yano, H. Kawakami, S. Yamasaki and Y. Kanno, “Caption Capturing Ability and the Potential Response of a Poly(o-Aminophenol) Film Electrode to Dissolved Ferric Ions,” Journal of the Electrochemical Society, Vol. 148, No. 2, 2001, pp. E61-E65. doi:10.1149/1.1339235
[19] A. Aramata, “Underpotential deposition, ,” In: J. O. M. Bockris, R. E. White and B. E. Conway, Eds., Modern Aspects of Electrochemistry, Vol. 31, Plenum Press, New York, 1997, Chapter 4, p. 112.
[20] K. Fuchs, “Electrical Resistance in Thin Metal Films,” Proceedings of the Cambridge Philosophical Society. Mathematical and Physical Sciences, Vol. 34, No. 1, 1938, pp. 100-193.
[21] E. H. Sondheimer, “Mean Free Path of Electrons in Metals,” Advances in Physics, Vol. 1, No. 1, 1952, pp. 1-42. doi:10.1080/00018735200101151
[22] P. Wissmann, “The Electrical Resistivity of Pure and Gas Covered Metal Films,” Zeitschrift für Physikalische Chemie, Vol. 71, No. 2, 1970, pp. 294-315.
[23] E. Dutkiewicz and P. Skoluda, “Adsorption of Benzenesulphonate Anions at an Au(111) Electrode: Application to Study of the Reconstruction Phenomena of the Au(100) Surface,” Journal of the Chemical Society, Faraday Transactions, Vol. 92, No. 20, 1996, pp. 3763-3767. doi:10.1039/ft9969203763
[24] “Tables of Interatomic Distances and Configurations in Molecules and Ions. The Chemical Society,” Burlington House, London, 1958.
[25] W. N. Hansen, “Electrode Resistance and the Emersed Double Layer,” Surface Science, Vol. 101, No. 1-3, 1980, pp. 109-122. doi:10.1016/0039-6028(80)90602-0
[26] D. L. Rath, “Studies of the Electrode Resistance in the Electrochemical Cell,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, No. 1-2, 1983, pp. 521-534. doi:10.1016/S0022-0728(83)80232-0
[27] P. G. De Gennes, “Polymers at an Interface; a Simplified View,” Advances in Colloids and Interface Science, Vol. 27, No. 1, 1987, pp. 189-209.
[28] G. Inzelt, M. Pineri, J. W. Schultze and M. A. Vorotyntsev, “Electron and Proton Conducting Polymers: Recent Developments and Prospects,” Electrochimica Acta, Vol. 45, No. 15-16, 2000, pp. 2403-2421. doi:10.1016/S0013-4686(00)00329-7
[29] T. Ikeda, R. Schmehl, P. Denisevich, K. Willman and R. W. Murray, “Permeation of Electroactive Solutes through ultrathin Polymeric Films on Electrode Surfaces,” Journal of the American Chemical Society, Vol. 104, No. 10, 1982, 2683-2691. doi:10.1021/ja00374a001
[30] P. Novák, K. Muller, K. S. V. Santhanami and O. Haas, “Electrochemically Active Polymers for Rechargeable Batteries,” Chemical Reviews, Vol. 97, No. 1, 1997, pp. 207-281. doi:10.1021/cr941181o

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.