Understanding the Impact of Different Types of Surface States on Photoelectrochemical Water Oxidation: A Microkinetic Modeling Approach

The oxygen evolution reaction (OER) has been identified as one of the performance-limiting processes in solar water splitting using photo-electrochemical (PEC) cells. One of the reasons for the low OER performance is related to the existence of different types of surface states at the semiconductor-electrolyte interface: recombining surface states (r-SS) and surface states due to intermediate species (i-SS). Since the impact of surface states on OER is still under debate, we investigate how different types of surface states affect PEC water oxidation and how they impact experimental measurements. In a new computational approach, we combine a microkinetic model of the OER on the semiconductor surface with the charge carrier dynamics within the semiconductor. The impact of r-SS and i-SS on the current-voltage curves, hole flux, surface state capacitance, Mott-Schottky plots, and chopped light measurements is systematically investigated. It is found that (a) r-SS results in a capacitance peak below the OER onset potential, while i-SS results in a capacitance peak around the onset potential; (b) r-SS leads to an increase in the OER onset potential and a decrease in the saturation current density; (c) r-SS leads to Fermi-level pinning before the onset potential, while i-SS does not result in Fermi-level pinning; and (d) a smaller capacitance peak of i-SS can be an indication of the lower catalytic performance of the semiconductor surface. Our approach in combination with experimental comparison allows distinguishing the impact of r-SS and i-SS in PEC experiments. We conclude that r-SS reduces the OER performance and i-SS mediates the OER.