Quantitative Determination the Role of the Intrabandgap States in Water Photooxidation over Hematite Electrodes

The intrabandgap states on the hematite (α-Fe₂O₃) electrodes are believed to play an important role in water photooxidation. Yet, it is not fully understood how the intrabandgap states are involved in the reaction. In this work, the intraband-gap states in water photooxidation on α-Fe₂O₃ electrodes are investigated by a combination of multiple (photo-) electrochemical techniques and operando spectroscopic methods. Two kinds of surface states are observed on the electrodes during water photooxidation, and their roles are quantitatively determined by the correlation with the steady-state photocurrent. It is demonstrated that the intrinsic electronic surface state close to the conduction band can act only as the recombination center for the photocarriers. However, the photogenerated surface state closer to the valence band is revealed to be the reactant in the rate-determining step in oxygen evolution reaction. These findings may be beneficial to elucidate the actual function of the surface states and provide insights into the kinetic and mechanism studies of water photooxidation on the α-Fe₂O₃ electrodes.