Oxygen electro-reduction on iron oxide electrodes. III: Heterogeneous catalytic H2O2 decomposition

Abstract Oxygen reduction on two well-defined iron oxide electrodes (γ-FeOOH and Fe3O4) shows deviations from linear Koutecky-Levich plots. These results can be explained by two limiting cases of the heterogeneous catalytic peroxide decomposition mechanism proposed by McIntyre (J. Phys. Chem., 71 (1967) 1196; J. Phys. Chem., 73 (1969) 4102). Recycling of oxygen by peroxide decomposition at the oxide surfaces depends on the relative magnitude of the peroxide decomposition rate (k4), the convective-diffusion flux ( Z p W 1 2 ) and the oxygen adsorption kinetics ( k 2 k −2 ).

[1]  Derek Pletcher,et al.  A study of cathodic oxygen reduction at platinum using microelectrodes , 1993 .

[2]  V. Vesovic,et al.  Rotating disk electrode: A re-examination of some kinetic criteria with a special reference to oxygen reduction , 1987 .

[3]  C. Bamford,et al.  Comprehensive Chemical Kinetics , 1976 .

[4]  E. Yeager,et al.  The Kinetics of the Oxygen Reduction Reaction on Gold in Alkaline Solution , 1978 .

[5]  M. Sluyters-Rehbach,et al.  On the rate equation of nucleation and the concept of active sites in electrodeposition , 1988 .

[6]  E. Calvo,et al.  Electrocatalysis of oxygen reduction at well-defined iron oxide electrodes , 1994 .

[7]  E. Calvo,et al.  Electrocatalysis of oxygen reduction at Fe3O4 oxide electrodes in alkaline solutions , 1992 .

[8]  J. McIntyre.  Kinetics of electrode processes with coupled heterogenous chemical catalytic reactions , 1967 .

[9]  K. Hashimoto,et al.  Anodic Deposition of Ferric Oxy‐Hydroxide Films on Platinum from Perchlorate Solutions , 1974 .

[10]  E. Calvo,et al.  THE REDUCTION OF HYDROGEN PEROXIDE ON PASSIVE IRON IN ALKALINE SOLUTIONS , 1984 .

[11]  H. Wroblowa,et al.  Mechanism and kinetics of oxygen reduction on steel , 1990 .

[12]  E. Yeager,et al.  A Mechanistic Study of O 2 Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes , 1980 .

[13]  T. Shimomura,et al.  Electrochemical responses of multiply-charged transition metal complexes bound electrostatically to graphite electrode surfaces coated with polyelectrolytes , 1980 .

[14]  Martin Stratmann,et al.  An electrochemical study of phase-transitions in rust layers , 1983 .

[15]  J. Bockris,et al.  Electrodes of conductive metallic oxides, Part A : edited by S. Trasatti, Elsevier, Amsterdam, 1980, $76.75, 366 pages. , 1983 .

[16]  J. McIntyre.  Kinetics of heterogeneous catalytic electrode reactions. II. Charge-transfer kinetics , 1969 .

[17]  U. Stimming.  Redox reactions at FeOOH deposition layers , 1982 .