Photoelectrochemical Methods for the Determination of the Flat-Band Potential in Semiconducting Photocatalysts: A Comparison Study

In addition to the band gap of a semiconducting photocatalyst, its band edges are important because they play a crucial role in the analysis of charge transfer and possible pathways of the photocatalytic reaction. The Mott-Schottky method using electrochemical impedance spectroscopy is the most common experimental technique for the determination of the electron potential in photocatalysts. This method is well suited for large crystals, but in the case of nanocatalysts, when the thickness of the charged layer is comparable with the size of the nanocrystals, the capacitance of the Helmholtz layer can substantially affect the measured potential. A contact between the electrolyte and the substrate, used for deposition of the photocatalyst, also affects the impedance. Application of other photoelectrochemical methods may help to avoid concerns in the interpretation of impedance data and improve the reliability of measurements. In this study, we have successfully prepared five visible-light active photocatalysts (i.e., N-doped TiO2, WO3, Bi2WO6, CoO, and g-C3N4) and measured their flat-band potentials using four (photo)electrochemical methods. The potentials are compared for all methods and discussed regarding the type of semiconducting material and its properties. The effect of methanol as a sacrificial agent for the enhanced transfer of charge carriers is studied and discussed for each method.