Revealing the Role of TiO₂ Surface Treatment of Hematite Nanorods Photoanodes for Solar Water Splitting

Ultrathin TiO2 is deposited on conventional hydrothermal grown hematite nanorod arrays by atomic layer deposition (ALD). Significant photoelectrochemical water oxidation performance improvement is observed when the ALD TiO2-treated samples are annealed at 650 °C or higher temperatures. The electrochemical impedance spectroscopy (EIS) study shows a surface trap-mediated charge transfer process exists at the hematite-electrolyte interface. Thus, one possible reason for the improvement could be the increased surface states at the hematite surface, which leads to better charge separation, less electron-hole recombination, and hence, greater improvement of photocurrent. Our Raman study shows the increase in surface defects on the ALD TiO2-coated hematite sample after being annealed at 650 °C or higher temperatures. A photocurrent of 1.9 mA cm(-2) at 1.23 V (vs RHE) with a maximum of 2.5 mA cm(-2) at 1.8 V (vs RHE) in 1 M NaOH under AM 1.5 simulated solar illumination is achieved in optimized deposition and annealing conditions.