Fig. 4
From: Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry
Kinetic factors mask the inversion of peak potentials and the true peak dispersion. Simulated voltammograms (25 mV s−1) showing the masking of the system’s electrostatic (i.e., diode and Frumkin effects) by slow kinetics. Curves are calculated using model 3 and by setting k et to either 100 s−1 (a) or 1 s−1 (b). Frumkin G was + 0.5 and \(\theta\) is adjusted from 0.04 in the anodic segment to 1.95 in the cathodic one. This increase in \(\theta\) reflects the ca. 50-fold drop in the (photo)hole opposition current (\(I_{\mathrm{L}}\)) generally required to fit experimental data. The y-axis current is expressed as \(\psi = \left( {I/I_{\mathrm{p,rev}}} \right) \times \left( {RT/\left( {Q_{\rm F}Fv} \right)} \right)\), with \(I_{\rm p,rev}\) being the peak current obtained for a fast charge-transfer process (see Supplementary Note 6 and Supplementary Fig. 14 for details)
