Photoelectrochemical impedance spectroscopy (PEIS) is a useful tool for the characterization of photoelectrodes for solar water splitting. However, the analysis of PEIS spectra often involves a priori assumptions that might bias the results. This work puts forward an empirical method that analyzes the distribution of relaxation times (DRT), obtained directly from the measured PEIS spectra of a model hematite photoanode. By following how the DRT evolves as a function of control parameters such as the applied potential and composition of the electrolyte solution, we obtain unbiased insights into the underlying mechanisms that shape the photocurrent. In a subsequent step, we fit the data to a process-oriented equivalent circuit model (ECM) whose makeup is derived from the DRT analysis in the first step. This yields consistent quantitative trends of the dominant polarization processes observed. Our observations reveal a common step for the photo-oxidation reactions of water and H2O2 in alkaline solution
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