WO3 layer sensitized with BiVO4 and MIL-101(Fe) as photoanode for photoelectrochemical water oxidation

Thick tungsten oxide layers were prepared electrophoretically in order to be used as photoanodes in photoelectrochemical water oxidation applications. The highest photocurrent density was obtained for a WO3 layer with thickness of similar to 900 nm. Additionally, WO3/BiVO4 and WO3/BiVO4/MIL-101(Fe) heterojunctions have been fabricated using WO3 layer as substrate. WO3/BiVO4 shows an increased value of the electrochemical active surface area indicating that more sites of this photoanode are activated through the formation of the heterojunction. The small V5+ signals observed in the V 2p XPS spectra of these heterojunctions were attributed to the substitution of V5+ atoms with W6+ atoms on the surface of BiVO4. Excessive W doping of the BiVO4 film determined the decrease of the photoelectrochemical performance of WO3/BiVO4 photoanode. The significant improvement of the photoconversion efficiency of the sample decorated with MIL-101(Fe) indicated that this cocatalyst provides sites more efficiently in the photoelectrochemical process. This performance was correlated with the reduced value of the charge transfer resistance at electrode/electrolyte interface obtained from electrochemical impedance spectroscopy investigation.