UV-Vis-Induced Degradation of Phenol over Magnetic Photocatalysts Modified with Pt, Pd, Cu and Au Nanoparticles

The combination of TiO₂ photocatalyst and magnetic oxide nanoparticles enhances the separation and recoverable properties of nanosized TiO₂ photocatalyst. Metal-modified (Me = Pd, Au, Pt, Cu) TiO₂/SiO₂@Fe₃O₄ nanocomposites were prepared by an ultrasonic-assisted sol-gel method. All prepared samples were characterized by X-ray powder diffraction (XRD) analysis, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Mott-Schottky analysis and photoluminescence spectroscopy (PL). Phenol oxidation pathways of magnetic photocatalysts modified with Pt, Pd, Cu and Au nanoparticles proceeded by generation of reactive oxygen species, which oxidized phenol to benzoquinone, hydroquinone and catechol. Benzoquinone and maleic acid were products, which were determined in the hydroquinone oxidation pathway. The highest mineralization rate was observed for Pd-TiO₂/SiO₂@Fe₃O₄ and Cu-TiO₂/SiO₂@Fe₃O₄ photocatalysts, which produced the highest concentration of catechol during photocatalytic reaction. For Pt-TiO₂/SiO₂@Fe₃O₄ nanocomposite, a lack of catechol after 60 min of irradiation resulted in low mineralization rate (CO₂ formation). It is proposed that the enhanced photocatalytic activity of palladium and copper-modified photocatalysts is related to an increase in the amount of adsorption sites and efficient charge carrier separation, whereas the keto-enol tautomeric equilibrium retards the rate of phenol photomineralization on Au-TiO₂/SiO₂@Fe₃O₄. The magnetization hysteresis loop indicated that the obtained hybrid photocatalyst showed magnetic properties and therefore could be easily separated after treatment process.