Understanding the Roles of NiOx in Enhancing the Photoelectrochemical Performance of BiVO4 Photoanodes for Solar Water Splitting

Abstract

Solar water oxidation is considered as a promising method for efficient utilization of solar energy and bismuth vanadate (BiVO₄ ) is a potential photoanode. Catalyst loading on BiVO₄ is often used to tackle the limitations of charge recombination and sluggish kinetics. In this study, amorphous nickel oxide (NiO_x ) is loaded onto Mo-doped BiVO₄ by photochemical metal-organic deposition method. The resulting NiO_x /Mo:BiVO₄ photoanodes demonstrate a two-fold improvement in photocurrent density (2.44 mA cm^-2 ) at 1.23 V versus reversible hydrogen electrode (RHE) compared with the uncatalyzed samples. After NiO_x modification the charge-separation and charge-transfer efficiencies improve significantly across the entire potential range. It is further elucidated by open-circuit photovoltage (OCP), time-resolved-microwave conductivity (TRMC), and rapid-scan voltammetry (RSV) measurements that NiO_x modification induces larger band bending and promotes efficient charge transfer on the surface of BiVO₄ . This work provides insight into designing BiVO₄ -catalyst assemblies by using a simple surface-modification route for efficient solar water oxidation.

Keywords: band bending; bismuth vanadate; charge transfer; photoelectrocatalysis; water splitting.