Abstract

Hematite photoanodes have shown potential for use in practical applications of photoelectrochemical (PEC) water splitting cells due to their abundance and stability, yet their efficiency needs to be improved. To optimize photoanode performance, co-catalysts such as amorphous nickel/iron oxyhydroxide layers are often deposited on the surface of hematite to enhance activity by catalyzing oxygen evolution. Recent studies have shown that the role of oxyhydroxide layers in changing PEC activity can vary depending on factors such as film morphology, co-catalyst layer thickness, and electrolyte composition. In this study, we investigate the effect of NiOOH and (Ni,Fe)OOH layers on the PEC activity of electrodeposited nanostructured hematite films. Our analysis of charge transfer and recombination rate constants determined from chronoamperometry and electrochemical impedance data suggests that the coatings' role is purely passivating, which is crucial for discontinuous electrodeposited films. Importantly, we show that the passivating properties of these coatings are enhanced by the presence of ppm concentrations of Fe in the electrolyte. We believe that our findings will be useful for further development of hematite photoanodes.

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