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Photoelectrocatalytic techniques have been developed for the removal of widely contaminated organic substances in the environment, especially the development of semiconductor film preparation on the electrode substrate. The main objective of this research is to develop the preparation of WO3/BiVO4 thin film on conductive glass (ITO) for application in photoelectrocatalytic cells to remove organic dyes. WO3 film fabrication on the ITO substrate was developed using an electrodeposition technique and then calcined at 500 °C for 30 min. The second BiVO4 film layer was immobilized on the ITO/WO3 surface using a dip coating method and calcination continued at 550 °C for 1 h. The optical properties and electrochemical resistance of the fabricated ITO/WO3/BiVO4 electrode were examined for use in oxidation of water solutions. The ITO/WO3/BiVO4 electrode was applied to the removal of organic dye under photocatalytic, electrocatalytic, and photoelectrocatalytic mechanisms. We succeeded in preparing the ITO/WO3/BiVO4 and understanding its characteristics and photoelectrocatalytic activities. We can confirm the absorption properties in the visible light, and the bandgap energy value of WO3 and BIVO4 of 2.8 and 2.4 eV, respectively. We found that immobilizing BiVO4 on the WO3 layer significantly increased the efficiency of the electron transfer rate at the interfacial electrode/electrolyte surface. Importantly, it can confirm the effectiveness of the removal of organic dyes in aqueous solutions under the PEC mechanism, which was 4 and 10 times higher than that of electrocatalytic and photocatalytic mechanism, respectively. This research can be further developed for use in a wastewater treatment system in the dye industry and in industries that produce other organic contaminants.
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