Proceedings of September Meeting 2016 (NFM16)
Publication date: 14th June 2016
The photoelectrochemical performance of bismuth vanadate (BiVO4) photoanode is limited by poor charge carrier efficiencies. Methods have been implemented to improve charge separation efficiency by doping, nanostructuring and co-catalyst loading. Former researchers who achieved high separation efficiency usually resort to fabricating nanostructures whose size smaller than the diffusion length, which often needs WO3 scaffold or complex fabrication procedure. Further efforts are still needed to develop a relatively simpler method in photoanode fabrication.
Here we develop the NiOx loaded BiVO4 photoanode based on gradient Mo doping through simple spin coating method. The bulk BiVO4 was spun coated layer by layer, forming a gradient Mo-doped content (Mo ratio 2% to 0% from bottom to top). Afterwards, a layer of transparent nickel oxide was loaded on the BiVO4 surface by photochemical metal-organic deposition method followed by annealing in the air. The morphology and optical properties showed no change after NiOx treatment. Photoanode with NiOx layer (NiOx/Mo:BiVO4) achieved a photocurrent density of 2.44 mA cm-2 at 1.23 V vs. RHE under AM 1.5 illumination, which is twice the value for photoanodes without NiOx (Mo:BiVO4) (1.2 mA cm-2). Both the charge separation efficiency and transport efficiency increased after the addition of NiOx, especially for separation efficiency it doubled to 50% at 1.23V vs RHE. The improvement of charge efficiencies implies the formation of heterojunction (NiOx-BiVO4), which could be responsible for increased photocurrent density and cathodically shifted onset potential by 70 mV. From open-circuit potential (OCP) measurements, the calculated carrier lifetime for NiOx/Mo:BiVO4 reduced from 0.3 s to 0.13 s, indicating the faster injection of carriers from photoanode to the electrolyte. It further confirmed the formation of heterojunction, enhancing charge movement across the bulk and through the interface. Furthermore, the NiOx/Mo:BiVO4 photoanode exhibited great stability for over 2 h in 0.5 M Na2SO4 under illumination. Our work gives insight into improving charge separation and charge transport of photoanodes by simple treatment with amorphous transparent NiOx film. Future work may focus on the optimal Ni ratio and treatment conditions to achieve better PEC performance.
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