The electrochemical oxidation and reduction of the
Cu1+/Cu2+ redox system at p-GaAs electrodes
have been
investigated by impedance spectroscopy. This reaction is a
diffusion-controlled process via the valence band,
which competes well with the anodic decomposition reaction. The
method of impedance spectroscopy makes
it possible to determine kinetic parameters such as the rate constants
for the oxidation and the reduction of
the redox system. In addition the shift of the flatband potential
and of the corresponding energy bands at the
GaAs−electrolyte interface could be followed during current flow.
In the case of this redox system the
potential dependence of the rates and of the interfacial current are in
agreement with the theory on charge
transfer kinetics at semiconductor electrodes. Above a
Cu1+ concentration of 4 mM the oxidation
current
increased linearly with the concentration, and the second-order rate
constant was determined to be
=
5.10-19 cm4 s-1.
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