Activating the surface and bulk of hematite photoanodes to improve solar water splitting

Abstract

A simple electrochemical activation treatment is proposed to improve effectively the photoelectrochemical performance of Nb,Sn co-doped hematite nanorods. The activation process involves an initial thrice cathodic scanning (reduction) and a subsequent thrice anodic scanning (oxidation), which modifies both the surface and bulk properties of the Nb,Sn:Fe₂O₃ photoanode. First, it selectively removes the surface components to different extents endowing the hematite surface with fewer defects and richer Nb–O and Sn–O bonds and thus passivates the surface trap states. The surface passivation effect also enhances the photoelectrochemical stability of the photoanode. Finally, more Fe²⁺ ions or oxygen vacancies are generated in the bulk of hematite to enhance its conductivity. As a result, the photocurrent density is increased by 62.3% from 1.88 to 3.05 mA cm⁻² at 1.23 V_RHE, the photocurrent onset potential shifts cathodically by ∼70 mV, and photoelectrochemical stability improves remarkably relative to the pristine photoanode under simulated sunlight (100 mW cm⁻²).