Silica-Driven Bandgap Engineering in Cobalt Ferrite Nanoparticles for Efficient Removal of Mercapto Contaminants Under Sunlight Irradiation

The degradation of mercapto organic contaminants is highly important for safety and environmental protection since the specific chemical properties and the strong nature of S-containing bonds can make them less susceptible to traditional degradation mechanisms compared to other types of organic bonds. Thus, degradation of mercapto organic contaminants often requires catalysts with specific bandgap properties to ensure efficient generation of reactive species and appropriate redox potential alignment. Hence, in this work, we prepared bandgap-engineered semiconductor photocatalysts based on nanoparticles of different silica-doped spinel cobalt ferrite [SiO2/CoFe2O4] (abbreviated as SiMCoF) [SiMCoF-1, SiMCoF-2, and SiMCoF-3] and characterized them by different analytical techniques. Since the dopant composition in a heterogeneous semiconductor material has important effects on its photocatalytic efficiency because adjusting the dopant profile can modulate impurity bands and enhance optical properties, which is crucial for the oxidative degradation of organic pollutants. Results from TEM, SEM, and their EDS analysis revealed that increased SiO2 content showed improved surface area in the matrix, facilitating the increased absorption of oxygen impurities. This is further observed by the higher Rmax values presented in AFM of SiMCoF-3 (139 nm) compared to SiMCoF-2 (116 nm) and SiMCoF-1 (8.78 nm), depicting its larger effective surface area (100 µm2), which in turn increases the active binding sites in the matrix. The Raman spectrum and XRD pattern of SiMCoF-3 showed various crystal planes with different atomic arrangements and a smaller crystallite size, leading to varying affinities for oxygen impurities. As a result, the optical bandgap decreased from 3.42 eV to 2.89 eV for SiMCoF-3, which is attributed to the quantum confinement effects caused by the smaller particle size and the dispersion of silica particles in the cobalt ferrite matrix. Thus, SiMCoF-3 showed elevated degradation performance without using any potential oxidants over the degradation of mercapto organic contaminants such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and thiophenol under sunlight irradiation compared to other ferrites, and showed better results than Fenton’s reagent.