Optimization of BiVO4 photoelectrodes made by electrodeposition for sun-driven water oxidation

In this work, the synthesis of cheap BiVO4 photoanodes for the photoelectrochemical water splitting reaction was optimized via the scalable thin film electrodeposition method. Factors affecting the photoelectrochemical activity, such as the electrodeposition time, the ratio of the Bi-KI to benzoquinone-EtOH in the deposition bath, and the calcination temperature, have been investigated by using the Central Composite Design of Experiments. Pristine monoclinic scheelite BiVO4 photoanodes having a photocurrent density of 0.45 ± 0.05mA/cm2 at 1.23 V vs RHE have been obtained. It was shown that a high photocurrent density is generally dictated by the following physico-chemical properties: a higher crystallite size, optimal thickness and a porous morphology, which give rise to a low charge transfer resistance, low onset potential and a high donor density. Moreover, to the best of our knowledge, this is the first report on the depth profile XPS analysis performed in BiVO4 photoanodes made by electrodeposition technique, from which it was concluded that the surface V species exist as V4+ while the bulk V species are V5+. The V4+ induces a higher amount of surface oxygen vacancies, which was found to be beneficial for the photoactivity.