Abstract
A method based on microelectrodes of ZnO single crystals was employed to determine the effective reaction velocity for dark reduction of ferrocenium acceptors by electrons from the semiconductor conduction band. Measurement techniques were explored and theoretical models for steady-state voltammetry at semiconductor electrodes developed. The microelectrode method as presented here represents an unambiguous experimental method for ascertaining ideal interfacial behavior even at high current flows found near the flatband potential. These results are compared with reaction velocities derived from extrapolation methods at millimeter-sized ZnO electrodes. It is seen that the extrapolation method is insensitive to nonideal behavior in the reduction reaction whereas the microelectrode method is not.
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