Journal
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
Volume 631, Issue 1-2, Pages 62-70Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2009.03.019
Keywords
Oxygen evolution; Impedance; Bode plot; Iron electrode; Cobalt electrode; Nickel electrode
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Although the mechanism for the oxygen evolution reaction (OER) is likely to be similar for oxidised electrodes of the adjacent transition metals Ni, Co and Fe, the electrochemical impedance spectra, recorded for each of these anodes during oxygen evolution in 1.0 M NaOH, are significantly different in appearance. This impedance data is analysed using an approach similar to that of Cahan and Chen [B.D. Cahan, C.T. Chen, J. Electrochem. Soc. 129 (1982) 700-705] in an earlier important article on this topic. A controversial proposal by these workers that OER Tafel slopes (measured by either ac or dc techniques) for many electrode systems are not in fact characteristic of the kinetics of the reaction, but instead of the potential dependent conductivity of the oxide, is dismissed on the basis of our data. In the case of Co, however, it is found that the kinetics of the OER are masked by a dominant low frequency pseudo-capacitance, arising most likely from a non-homogeneous surface charge distribution associated with the oxidation of Co(III)Co(IV) oxy-hydroxide species. A consistent interpretation of the data is provided, which envisages that Fe exhibits the most general impedance response with the spectra for the other anodes taking the form of limiting cases. Consideration is also given to the most appropriate choice of equivalent circuit model (with a firm physical basis) to aid our understanding of the complex interface at which oxygen evolution proceeds. (C) 2009 Elsevier B.V. All rights reserved.
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