Abstract
The rate of charge transport of electrodes modified with osmium containing poly(N-vinylimidazole) has been examined as a function of the nature of the contacting electrolyte solution and of temperature. Heterogeneous electron transfer from the electrode into the polymer film has also been investigated. The charge transport parameters show that the nature of the electrolyte anion and its concentration have a large impact on the polymer morphology. In sulfuric acid the films appear significantly swollen, hydrated, and porous, while in perchlorate-containing solutions they are rather compact. Activation energies for the rate-determining step of charge transport show that, depending on the electrolyte, segmental chain motion or ion movement represents the rate-limiting process.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. R. Hillman, inElectrochemical Science and Technology of Polymers, R. G. Linford, ed. (Elsevier Applied Science, Amsterdam, 1987), Vol. 1, Chap. 5, p. 103.
R. W. Murray, inElectroanalytical Chemistry, A. J. Bard, ed. (Dekker, New York, 1983), Vol. 13, p. 191.
L. R. Faulkner,Electrochim. Acta 34, 1699 (1989).
G. Inzelt,Electrochim. Acta 34, 83 (1989).
A. H. Schroeder and F. B. Kaufman,J. Electroanal. Chem. 113, 209 (1980).
F. B. Kaufman, A. H. Schroeder, E. M. Engler, S. R. Kramer, and J. Q. Chambers,J. Am. Chem. Soc. 102, 483 (1980).
C. H. Bamford and E. Schofield,Polymer 22, 1227 (1981).
D. A. Buckingham, F. P. Dwyer, H. A. Goodwin, and A. M. Sargeson,Aust. J. Chem. 17, 325 (1964).
R. J. Forster and J. G. Vos,Macromolecules 23, 4372 (1990).
E. M. Kober, J. V. Caspar, B. P. Sullivan, and T. J. Meyer,Inorg. Chem. 27, 4587 (1988).
K. M. O'Connell, E. Waldner, L. Roullier, and E. Laviron,J. Electroanal. Chem. 162, 77 (1984).
K. Aoki, K. Tokuda, and H. Matsuda,J. Electroanal. Chem. 146, 417 (1983).
K. J. Vetter,Electrochemical Kineties (Academic Press, New York and London, 1987), p. 107.
H. Matsuda,Bull. Chem. Soc. Jpn. 53, 3439 (1980).
J. Q. chambers and G. Inzelt,Anal. Chem. 57, 1117 (1985).
G. Inzelt, L. Szabo, J. Q. Chambers, and R. W. Day,J. Electroanal. Chem. 201, 301 (1988).
T. Ohsaka, H. Yamamoto, and N. Oyama,J. Phys. Chem. 91, 3775 (1987).
M. E. G. Lyons, H. G. Fay, J. G. Vos, and A. J. Kelly,J. Electroanal. Chem. 250, 207 (1988).
R. J. Forster, M. E. G. Lyons, and J. G. Vos, Submitted for publication.
P. Daum, J. R. Lenhard, D. Rolison, and R. W. Murray,J. Am. Chem. Soc. 102, 4649 (1980).
B. A. White and R. W. Murray,J. Am. Chem. Soc. 109, 2576 (1987).
J. C. Jernigan and R. W. Murray,J. Am. Chem. Soc. 109, 1738 (1987).
M. E. G. Lyons, H. G. Fay, T. McCabe, J. Corish, J. G. Vos, and A. J. Kelly,J. Chem. Soc., Faraday Trans. 86, 2905 (1990).
Y. Marcus,Ion Solvation (Wiley-Interscience, New York, 1985).
K. Doblhofer and R. D. Armstrong,Electrochim. Acta 33, 453 (1988).
R. J. Forster, A. J. Kelly, J. G. Vos, and M. E. G. Lyons,J. Electroanal. Chem. 270, 365 (1989).
P. Ferruti and R. Barbucci,Adv. Polym. Sci. 58, 55 (1984).
G. Inzelt, J. Backsai, J. Q. Chambers, and R. W. Day,J. Electroanal. Chem. 201, 301 (1986).
S. M. Oh and L. R. Faulkner,J. Am. Chem. Soc. 111, 5613 (1989).
E. F. Bowden, M. F. Dautartas, and J. F. Evans,J. Electroanal. Chem. 219, 91 (1987).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Forster, R.J., Vos, J.G. Charge transport properties of poly(N-vinylimidazole) containing [Os(N)6]2+/3+ moieties. J Inorg Organomet Polym 1, 67–86 (1991). https://doi.org/10.1007/BF00701030
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00701030