Photoelectrochemical Water Oxidation by Cobalt Catalyst (“Co−Pi”)/α-Fe2O3 Composite Photoanodes: Oxygen Evolution and Resolution of a Kinetic Bottleneck

Abstract

A cobalt−phosphate water oxidation catalyst (“Co−Pi”) has been electrodeposited onto mesostructured α-Fe₂O₃ photoanodes. The photoelectrochemical properties of the resulting composite photoanodes were optimized for solar water oxidation under frontside illumination in pH 8 electrolytes. A kinetic bottleneck limiting the performance of such photoanodes was identified and shown to be largely overcome by more sparse deposition of Co−Pi onto the α-Fe₂O₃. Relative to α-Fe₂O₃ photoanodes, a sustained 5-fold enhancement in the photocurrent density and O₂ evolution rate was observed at +1.0 V vs RHE with the Co−Pi/α-Fe₂O₃ composite photoanodes. These results demonstrate that integration of this promising water oxidation catalyst with a photon-absorbing substrate can provide a substantial reduction in the external power needed to drive the catalyst’s electrolysis chemistry.