Abstract
Results of research into structural and electrocatalytic properties of metalloporphyrins and metallophthalocyanines pyrolyzed on carbon supports of various dispersion degree in the oxygen electroreduction reaction (OER) are analyzed. The pyrolysis products (pyropolymers) that form at T ≤ 800°С in inert atmosphere contain centers Co(Fe)–N surrounded by carbon particles. The oxygen electroreduction reaction on pyropolymers in acid and alkali solutions is studied on a model gas-diffusion electrode and a rotating ring–disk electrode. The slopes of Tafel plots in an acid solution are 60 and 120 mV. On a disk electrode covered with a pyropolymer, the intermediate product of OER, hydrogen peroxide, is fixed on the ring electrode throughout the entire range of OER potentials. The activity of pyropolymers in the hydrogen peroxide electroreduction reaction in an acid solution is insignificant. In an acid environment, OER occurs via a parallel–successive mechanism with a slow stage of the attachment of the first electron. In alkali media, slopes of Tafel plots equal 40 and 120 mV at low and high polarizations, respectively. The amount of hydrogen peroxide fixed on the ring electrode corresponds to 2–5% of the disk electrode current. A pyropolymer is active in the hydrogen peroxide reduction. The slow stage in OER in an alkali environment is the attachment of the second electron at a low polarization and the attachment of the first electron, at a high polarization. In acid and alkali solutions a pyropolymer is methanol-tolerant.
Similar content being viewed by others
REFERENCES
Wang, J.T., Wasmus, S., and Savinell, R.F., J. Electro-chem. Soc., 1996, vol. 143, p. 1233.
Radyushkina, K.A. and Tarasevich, M.R., Elektrokhimiya, 1986, vol. 22, p. 1155.
Tarasevich, M.R. and Radyushkina, K.A., Mater. Chem. Phys., 1989, vol. 22, p. 477.
Scherson, D., Tanaka, A.A., Gupta, S.L., Tryk, D., Fierro, C., Holze, R., Yeager, E.B., and Lattimer, R.P., Electrochim. Acta, 1986, vol. 31, p. 1247.
Lalande, G., Côté, R., Tamizhmani, G., Guay, D., Dodelet, J.P., Dignard-Bailey, L., Weng, L.T., and Bertrand, P., Electrochim. Acta, 1995, vol. 40, p. 2635.
Faubert, G., Lalande, G., Côté, R., Guay, D., Dodelet, J.P., Weng, L.T., Bertrand, P., and Denes, G., Electrochim. Acta, 1996, vol. 41, p. 1689.
Van der Putter, A., Elzing, A., Visscher, W., and Barendrecht, E., J. Electroanal. Chem., 1986, vol. 205, p. 233.
Sawaguchi, T., Itabachi, T., Matsue, T., and Uchida, I., J. Electroanal. Chem., 1990, vol. 279, p. 219.
Okada, T., Gokita, M., Yuasa, M., and Sekine, I., J. Electrochem. Soc., 1998, vol. 145, p. 815.
Faubert, G., Côté, R., Guay, D., Dodelet, J.P., Dénés, G., and Bertrand, P., Electrochim. Acta, 1998, vol. 43, p. 341.
Goiković, S.Lj., Gupta, S., and Savinell, R.F., J. Electrochem. Soc., 1998, vol. 145, p. 3493.
Lalande, G., Côté, R., Guay, D., and Dodelet, J.P., Electrochim. Acta, 1997, vol. 42, p. 1379.
Bouwkamp-Wijnoltz, A.L., Visscher, W., and Van Veen, A.R., Electrochim. Acta, 1998, vol. 43, p. 3141.
Tyurin, V.S., Radyushkina, K.A., Levina, O.A., and Tarasevich, M.R., Elektrokhimiya, 2001, vol. 37, p. 981; Radyushkina, K.A., Tarasevich, M.R., Novikova, E.M., and Kublanovskii, V.S., Ukr. Khim. Zh., 1986, vol. 52, p. 38.
Tyurin, V.S., Bogatyreva, G.P., Zhutaeva, G.V., Korovin, N.V., Marinich, M.A., Radyushkina, K.A., Tarasevich, M.R., and Yuskov, A.Yu., Elektrokhimiya, 2001, vol. 37, p. 1250.
Zhutaeva, G.V., Radyushkina, K.A., Marinich, M.A., Bogatyreva, G.P., and Tarasevich, M.R., Elektrokhimiya, 2001, vol. 37, p. 1223.
Claude, E., Addou, T., Latour, J.M., and Aldebert, P., J. Appl. Electrochem., 1998, vol. 28, p. 57.
Jiang, R. and Chu, D., J. Electrochem. Soc., 2000, vol. 147, p. 4605.
Faubert, G., Côté, R., Guay, D., Dodelet, J.P., Dénés, G., Poleunis, C., and Bertrand, P., Electrochim. Acta, 1998, vol. 43, p. 1969.
Gojkovic, S.Lj., Gupta, S., and Savinell, R.F., Electrochim. Acta, 1999, vol. 45, p. 889.
Gouérec, P., Savy, M., and Riga, J., Electrochim. Acta, 1998, vol. 43, p. 743.
Gouérec, P. and Savy, M., Electrochim. Acta, 1999, vol. 44, p. 2653.
Contamin, O., Debiemme-Chouvy, C., Savy, M., and Scarbeck, G., J. New Mater. Electrochem. Syst., 2000, vol. 3, p. 67.
Shukla, A.K., Manoharan, R., Paliteiro, C., Hamnett, A., and Goodenough, J.B., J. Appl. Electrochem., 1985, vol. 15, p. 774.
Savy, M., Coowar, F., Riga, J., Verbist, J.J., Bronoel, G., and Besse, S., J. Appl. Electrochem., 1990, vol. 20, p. 260.
Van Veen, J.A.R. and Van Baar, J.F., Rev. Inorg. Chem., 1982, vol. 4, p. 293.
Van Veen, J.A.R., Van Baar, J.F., and Kroese, C.I., Ber. Bunsen-Ges. Phys. Chem., 1981, vol. 85, p. 693.
Kiros, L. and Schwartz, S., J. Power Sources, 1991, vol. 36, p. 547.
Gouerec, P., Bilou, A., Contamin, O., Scarbeck, G., Savy, M., Barbe, J.M., and Guilard, R., J. Electroanal. Chem., 1995, vol. 398, p. 67.
Shteinberg, G.V., Kukushkina, I.A., Tarasevich, M.R., and Bagozky, V.S., Elektrokhimiya, 1981, vol. 17, p. 234.
Tarasevich, M.R., Khrushcheva, E.I., and Filinovskii, V.Yu., Vrashchayushchiisya diskovyi elektrod s kol'tsom (The Rotating Ring–Disk Electrode), Moscow: Nauka, 1987.
Bagozky, V.S., Tarasevich, M.R., and Filinovskii, V.Yu., Elektrokhimiya, 1969, vol. 5, p. 1218.
Tarasevich, M.R., Radyushkina, K.A., and Burshtein, R.Kh., Elektrokhimiya, 1970, vol. 6, p. 372.
Wroblova, H.S., Pan, Y.C., and Razumney, G., J. Electroanal. Chem., 1976, vol. 69, p. 195.
Tarasevich, M.R., Elektrokhimiya uglerodnykh materialov (The Electrochemistry of Carbonaceous Materials), Moscow: Nauka, 1984.
Randin, J.P. and Yeager, E.B., J. Electroanal. Chem., 1972, vol. 36, p. 257.
Xu, J., Huang, W., and McGreery, R.L., J. Electroanal. Chem., 1996, vol. 410, p. 235.
Salitza, G., Soffer, A., Eliad, L., Cohen, Y., and Aurbach, D., J. Electrochem. Soc., 2000, vol. 147, p. 2486.
Lin, C., Ritter, J.A., and Popov, B.N., J. Electrochem. Soc., 1999, vol. 146, p. 3639.
Burshtein, R.Kh., Vilinskaya, V.S., Zagudaeva, N.M., and Tarasevich, M.R., Elektrokhimiya, 1974, vol. 10, p. 1094.
Gottesfeld, S., Raistrick, I.D., and Srinivasan, S., J. Electrochem. Soc., 1987, vol. 134, p. 1455.
Zecevick, S.K., Wainright, J.S., Litt, M.H., Gojkovi, S.L., and Savinell, R.F., J. Electrochem. Soc., 1997, vol. 144, p. 2973.
Jiang, R. and Anson, F.C., J. Electroanal. Chem., 1991, vol. 305, p. 171.
Itoe, R.N., Wesson, G.D., and Kalu, E.E., J. Electrochem. Soc., 2000, vol. 147, p. 2445.
Solubilities of Inorganic and Metal Organic Com-pounds, Linke, W.E., Ed., Washington (DC), 1965, vol. 2.
Tyurin, V.S., Tarasevich, M.R., Radina, M.V., Marinich, M.A., Bogatyreva, G.P., and Zhutaeva, G.V., Abstracts of Papers, 53rd Ann. ISE Meet., September 15–20, 2002, Dusseldorf, Symp. 8, no. 4015.
Tamizhmani, G. and Dodelet, J.P., J. Electrochem. Soc., 1994, vol. 141, p. 41.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tarasevich, M.R., Radyushkina, K.A. & Zhutaeva, G.V. Electrocatalysis of the Oxygen Reaction by Pyropolymers of N4 Complexes. Russian Journal of Electrochemistry 40, 1174–1187 (2004). https://doi.org/10.1023/B:RUEL.0000048651.78377.5c
Issue Date:
DOI: https://doi.org/10.1023/B:RUEL.0000048651.78377.5c