Band engineering is employed thoroughly and targets technologically scalable photoanodes for solar water splitting applications. Complex and costly recipes are necessary, often for average performances. Here, we report simple photoanode growth and thermal annealing with effective band engineering results. By comparing Ti-doped hematite photoanodes annealed under nitrogen to photoanodes annealed in air, we found a strongly enhanced photocurrent of more than 200% in the first case. Using electrochemical impedance spectroscopy and synchrotron X-ray spectromicroscopy, we demonstrate that oxidized surface states and increased density of charge carriers are responsible for the enhanced photoelectrochemical (PEC) activity. Surface states are found to be related to the formation of pseudo-brookite clusters by surface Ti segregation. Spectro-ptychography is used for the first time at the Ti L3 absorption edge to isolate Ti chemical coordination arising from pseudo-brookite cluster contribution. Correlated with electron microscopy investigation and density functional theory calculations, the synchrotron spectromicroscopy data unambiguously prove the origin of enhanced PEC activity of N2-annealed Ti-doped hematite nanorods. Finally, we present here a handy and cheap surface engineering method beyond the known oxygen vacancy doping, allowing a net gain in the PEC activity for the hematite-based photoanodes.
Keywords: hematite photoanodes; oxygen vacancies; soft X-ray ptychography; solar water splitting; spectromicroscopy; surface states.