Identifying Water Oxidation Mechanisms at Pure and Titanium-Doped Hematite-Based Photoanodes with Spectroelectrochemistry

Investigation of the mechanism of the water oxidation reaction for hematite photoanodes has been one of the most persistently pursued topics in the course of understanding photoelectrochemical water splitting by transition metal oxides. Unfortunately, existing experimental techniques often require over-simplified models and theories that assume only one reaction path. In this work, however, it is proposed that water oxidation on hematite can proceed via mixed reaction paths according to spectroelectrochemical results without a priori assumptions. The true absorption signals of surface states responsible for water oxidation are isolated from subsidiary signals for undoped and Ti-doped hematite and contrasted with those of inactive species. The evolution of absorption signals as a function of applied potential and illumination intensity highlights the non-negligible contribution of direct hole transfer, especially for highly doped hematite.