Efficient photoelectrochemical water splitting over anodized p-type NiO porous films.

NiO photocathodes were fabricated by alkaline etching-anodizing nickel foil in an organic-based electrolyte. The resulting films have a highly macroporous surface structure due to rapid dissolution of the oxide layer as it is formed during the anodization process. We are able to control the films' surface structures by varying the anodization duration and voltage. With an onset potential of +0.53 V versus the reversible hydrogen electrode (RHE), the photocurrent efficiency of the NiO electrodes showed dependencies on their surface roughness factor, which determines the extent of semiconductor-electrolyte interface and the associated quality of the NiO surface sites. A maximum incident photon-to-current conversion efficiency (IPCE(max)) of 22% was obtained from NiO film with a roughness factor of 8.4. Adding an Al2O3 blocking layer minimizes surface charge recombination on the NiO and hence increased the IPCE(max) to 28%. The NiO/Al2O3 films were extremely stable during photoelectrochemical water splitting tests lasting up to 20 h, continuously producing hydrogen and oxygen in the stoichiometric 2:1 ratio. The NiO/Al2O3 and NiO films fabricated using the alkaline anodization process produced 12 and 6 times as much hydrogen, respectively, as those fabricated using commercial NiO nanoparticles.