Modelling Electrocatalytic Reactions on Rotating Disk Electrodes

 Milivoj Lovrić Milivoj Lovrić
Российский электрохимический журнал
Abstract / Full Text

Kinetic currents caused by the interaction of dissolved catalyst and substrate are calculated. Sigmoidal dependence of currents on the bulk concentration of catalyst can be tested and the rate constant of redox reaction can be calculated by the proposed method. The applicability limits are discussed.

Author information
  • 10090, Zagreb, Croatia

    Milivoj Lovrić

  1. Nicholson, R.S. and Shain, I., Theory of stationary electrode polarography. Single scan and cyclic methods applied to reversible, irreversible and kinetic systems, Anal. Chem., 1964, vol. 36, p. 706.
  2. Saveant, J.M. and Vianello, E., Potential-sweep chronoamperometry: kinetic currents for first-order chemical reaction parallel to electron-transfer process (catalytic current), Electrochim. Acta, 1965, vol. 10, p. 905.
  3. Feldberg, S.W. and Campbell, J.F., The quasicatalytic mechanism: a variation of the catalytic (EC') mechanism, Anal. Chem., 2009, vol. 81, p. 8797.
  4. Compton, R.G., Fisher, A.C., and Spackman, R.A., Homogeneous catalysis of electrochemical reactions. Channel electrode voltammetry and EC' mechanism, Electroanalysis, 1992, vol. 4, p. 167.
  5. Molina, A., Analytical solution corresponding to the i/t response to a multipotential step for a catalytic mechanism, J. Electroanal. Chem., 1998, vol. 443, p. 163.
  6. Davčeva, M., Mirčeski, V., and Komorsky-Lovrić, Š., Evaluation of the antioxidative activity by measuring the rate of the homogeneous oxidation reaction with ferroceniumdimethanol cation. Comparative analysis of glutathione and ascorbic acid, Int. J. Electrochem. Sci., 2011, vol. 6, p. 2718.
  7. Čižmek, L. and Lovrić, M., Simulation of electrocatalytic mechanism followed by chemical reaction, J. Electroanal. Chem., 2016, vol. 768, p. 129.
  8. Galvez, J., Molina, A., and Serna, C., Pulse polarography: part IX. A method of discriminationbetween the catalytic, CE, ECE and EC mechanism. Calculations of the rate constants of the chemical reaction for the catalytic, CE and ECE mechanism, J. Electroanal. Chem., 1981, vol. 124, p. 201.
  9. Senthamarai, R. and Rajendran, L., A comparison of diffusion-limited currents at microelectrodes of various geometries for EC' reactions, Electrochim. Acta, 2008, vol. 53, p. 3566.
  10. Zeng, J. and Osteryoung, R.A., Square wave voltammetry for a pseudo-first-order catalytic process, Anal. Chem., 1986, vol. 58, p. 2766.
  11. Andrieux, C.P., Dumas-Bouchiat, J.M., and Saveant, J.M., Catalysis of electrochemical reactions at derivatized electrodes. Kinetic model for stationary voltammetric techniques and preparative scale electrolysis, J. Electroanal. Chem., 1981, vol. 123, p. 171.
  12. Barker, P.D., Hill, H.A.O., and Walton, N.J., Fast second order electron transfer reactions coupled to redox protein electrochemistry. Experiment and digital simulation, J. Electroanal. Chem., 1989, vol. 260, p. 303.
  13. Gerbino, L., Baruzzi, A. M., and Iglesias, R.A., Catalytic EC' reaction at a thin film modified electrode, Electrochim. Acta, 2013, vol. 88, p. 66.
  14. Mirčeski, V. and Gulaboski, R., Surface catalytic mechanism in square wave voltammetry, Electroanalysis, 2001, vol. 13, p. 1326.
  15. Oyama, N., Sato, K., and Matsuda, H., Catalysis of electrode processes by octacyanomolibdenum(IV/V) complex bound electrostatically to graphite electrode coated with polyelectrolytes, J. Electroanal. Chem., 1980, vol. 115, p. 149.
  16. Karim-Nezhad, G., Hasanzadeh, M., Saghatforoush, L., Shadjou, N., Earshad, S., and Khalilzadeh, B., Kinetic study of electrocatalytic oxidation of carbohydrates on cobalt hydroxide modified glassy carbon electrode, J. Brazil. Chem. Soc., 2009, vol. 20, p. 141.
  17. Compton, R.G., Laing, M.E., Mason, D., Northing, R.J., and Unwin, P.R., Rotating disk electrodes: the theory of chronoamperometry and its use in mechanistic investigations, Proc. R. Soc. A, 1988, vol. 418, p. 113.
  18. Saveant, J.M. and Vianello, E., Potential-sweep voltammetry: general theory of chemical polarization, Electrochim. Acta, 1967, vol. 12, p. 629.
  19. Ward, K.R., Lawrence, N.S., Hartshorne, R.S., and Compton, R.G., Cyclic voltammetry of the EC' mechanism at hemispherical particles and their arrays: the split wave, J. Phys. Chem. C, 2011, vol. 115, p. 11204.
  20. Molina, A., Serna, C., and Martinez-Ortiz, F., Square wave voltammetry for a pseudo-first-order catalytic process at spherical electrodes, J. Electroanal. Chem., 2000, vol. 486, p. 9.
  21. Molina, A., Gonzalez, J., Laborda, E., Wang, Y., and Compton, R.G., Analytical theory of the catalytic mechanism in square wave voltammetry at disc electrodes, Phys. Chem. Chem. Phys., 2011, vol. 13, p. 16748.
  22. Gulaboski, R. and Mirčeski, V., New aspects of the electrochemical-catalytic (EC') mechanism in square wave voltammetry, Electrochim. Acta, 2015, vol. 167, p. 219.
  23. Gorton, L., Torstensson, A., Jaegfeldt, H., and Johansson, G., Electrocatalytic oxidation of reduced nicotinamide coenzymes by graphite electrodes modified with an adsorbed phenoxazinium salt, meldola blue, J. Electroanal. Chem., 1984, vol. 161, p. 103.
  24. Romero, M.R., Ahumada, F., Garay, F., and Baruzzi, A.M., Amperometric biosensor for direct blood lactate detection, Anal. Chem., 2010, vol. 82, p. 5568.
  25. Vorotyntsev, M.A., Konev, D.V., and Tolmachev, Y.V., Electroreduction of halogen oxoanions via autocatalytic redox mediation by halide anions: novel EC'' mechanism. Theory for stationary 1D regime, Electrochim. Acta, 2015, vol. 173, p. 779.
  26. Vorotyntsev, M.A. and Antipov, A.E., Reduction of bromate anion via autocatalytic redox-mediation by Br2/Br-redox couple. Theory for stationary 1D regime. Effect of different Nernst layer thickness for reactants, J. Electroanal. Chem., 2016, vol. 779, p. 146.
  27. Antipov, A.E. and Vorotyntsev, M.A., Maximum current density in the reduction of the bromate anion on a rotating disk electrode: asymptotic behaviour at large thickness of the diffusion layer, Russ. J. Electrochem., 2018, vol. 54, p. 186.
  28. Korotkova, E.I., Karbainov, Y.A., and Shevchuk, A.V., Study of antioxidant properties by voltammetry, J. Electroanal. Chem., 2002, vol. 518, p. 56.
  29. Korotkova, E.I., Karbainov, Y.A., and Avramchik, O.A., Investigation of antioxidant and catalytic properties of some biologically active substances by voltammetry, Anal. Bioanal. Chem., 2003, vol. 375, p. 465.
  30. Lowinsohn, D., Lee, P.T., and Compton, R.G., Towards detection of the total antioxidant concentrations of glutathione, cysteine, homocysteine and ascorbic acid using a nanocarbon paste electrode, Int. J. Electrochem. Sci., 2014, vol. 9, p. 3458.
  31. Compton, R.G., Day, M.J., Laing, M.E., Northing, R.J., Penman, J.I., and Waller, A.M., Rotating-disc electrode voltammetry. The catalytic mechanism (EC') and its nuances, J. Chem. Soc. Faraday Trans. 1, 1988, vol. 84, p. 2013.
  32. Andrieux, C.P., Dumas-Bouchiat, J.M., and Saveant, J.M., Catalysis of electrochemical reactions at redox polymer electrodes: effect of the film thickness, J. Electroanal. Chem., 1980, vol. 114, p. 159.
  33. Koutecky, J. and Levich, V.G., The use of a rotating disk electrode in the studies of electrochemical kinetics and electrolytic processes, Zh. Fiz. Khim., 1956, vol. 32, p. 1565.
  34. Treimer, S., Tang, A., and Johnson, D.C., A consideration of the application of Koutecky–Levich plots in the diagnoses of charge-transfer mechanism at rotating disk electrodes, Electroanalysis, 2002, vol. 14, p. 165.
  35. Strutwolf, J. and Schoeller, W.W., Linear and cyclic sweep voltammetry at a rotating disk electrode. A digital simulation, Electroanalysis, 1996, vol. 8, p. 1034.
  36. Hale, J.M., Transients in convective systems: I. Theory of galvanostatic, and galvanostatic with current reversal transients, at a rotating disk electrode, J. Electroanal. Chem., 1963, vol. 6, p. 187.
  37. Hale, J.M., Transients in convective systems: II. Limiting current and kinetically complicated galvanostatic transients at a rotating disc electrodes, J. Electroanal. Chem., 1964, vol. 8, p. 332.