Photoelectrocatalytic degradation of organic micropollutants with BiVO<sub>4</sub>/(TiO<sub>2</sub>/GO)<sub>mix</sub> ternary composite photoanodes

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In the recent decade, a wide range of emerging contaminants (ECs) has been regularly detected in the wastewater treatment plants (WWTPs) effluent, surface water and even groundwater. Among all these ECs, organic micropollutants (OMPs) are receiving increasing attention due to their characteristics of low concentration, difficulty in degradation and their harmful effects on humans and the environment. Nineteen OMPs have been included on the contaminant watch list of the European Union Water Framework Directive since 2015 and efficient and reliable methods to eliminate them are researched worldwide. Therefore, in this study, five of these 19 OMPs (benzotriazole (BTA), carbamazepine (CBZ), diclofenac (DIC), ketoprofen (KET) and caffeine (CAF)) were selected as target OMPs. And the research objective is to fabricate a ternary composite photoanode and to investigate its photoelectrocatalytic degradation performance for all five target OMPs.

BiVO4/(TiO2/graphene oxide (GO))mix ternary composite thin films were successfully deposited on fluorine-doped tin oxide (FTO) glass substrates using ultrasonic spray paralysis (USP) method to form a ternary heterojunction structure and to improve the photoelectrocatalytic performance for degradation of the five target OMPs. The morphology, crystal phase, surface chemical composition, optical and electrochemical properties of this ternary composite photoanode were analyzed by scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, incident photon-to-electron conversion efficiency (IPCE), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS), respectively. The results of these analyses showed that TiO2 P25 nanoparticles and GO sheets were distributed uniformly on the brain-shaped BiVO4 structure which indicated that the ternary heterojunction structure was formed successfully. From the UV-vis analysis, it could be estimated that the band gap energy for BiVO4/(TiO2/GO)mix ternary composite photoanodes is 2.43 eV. Further, the LSV and EIS analysis showed that the photocurrent of the ternary composite photoanodes is lower than pure BiVO4 photoanodes.
The degradation experiments were divided into five stages. The optimal photoanode type was first determined in the pre-experiment stage using methylene blue (MB) as indicator organic pollutant and then the effect of initial concentrations of target OMPs and initial pH on the degradation efficiency were studied in stage II and III, respectively. The highest removal efficiency of the five target OMPs was obtained with initial OMPs concentration at 10 μg·L-1 and initial pH range of 3.5-4.0. The degradation experiments were triplicated under this optimal condition in stage IV. It was noticed from the results that the degradation efficiency of different OMPs after 3 hours of reaction time varied from 31.1 % to 99.5 %. To further confirm that there is competition between the five target OMPs during the photoelectrocatalytic degradation process, experiments were carried out in which individual OMPs were degraded independently. The reusability and stability of the photoanodes were evaluated in stage V. Trapping experiments using scavengers were also included in this stage, which showed that superoxide anions was the most active species during the degradation process.