Correlation of photocurrent-voltage curves with flat-band potential for stable photoelectrodes for the photoelectrolysis of water

Using the differential capacitance technique, the flat-band potential of n-type TiO2, SnO2, SrTiO3, KTaO3, and KTa(0.77)Nb(0.23)O3 electrodes has been determined as a function of pH in aqueous electrolytes. Plots of flat-band potential vs. pH are linear in all cases and have a slope of approximately 0.059 V/pH unit. The flat-band potential correlates nicely with the onset for photoanodic currents corresponding to O2 evolution at the n-type semiconductor and H2 at the dark Pt cathode. The ordering of flat-band potentials at a given pH is SrTiO3 of the order of KTaO3 of the order of KTa(0.77)Nb(0.23)O3 greater than TiO2 greater than SnO2 (SnO2 most positive vs a saturated calomel electrode).