Preparation of Ho-Doped ZnO Powders by Sol–Gel and Hydrothermal Routes and Their Tribocatalytic Performance in Paracetamol Degradation
Stefani Petrova, Albena Bachvarova-Nedelcheva, Ralitsa Mladenova, Simona Delibaltova, Hristo Kolev, Nina KanevaIn this study, pure ZnO and Ho-doped ZnO powders (1 and 2 mol % Ho) were synthesized via hydrothermal and sol–gel methods and evaluated for their tribocatalytic activity toward the degradation of paracetamol, an emerging pharmaceutical contaminant in aquatic environments. Structural, morphological, and optical properties of the obtained materials were investigated by X-ray diffraction (XRD), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDS), ultraviolet–visible (UV–Vis) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy. SEM observations revealed pronounced morphology differences between the synthesis routes, with hydrothermally prepared samples exhibiting well-defined rod-like structures. XPS and EPR analyses provided evidence for successful Ho modification of ZnO and the presence of defect-related electronic states associated with Ho doping. The tribocatalytic performance was examined in distilled, tap, and mineral water using friction rods with different geometries in order to assess the influence of synthesis route, Ho concentration, and water composition. Among all the investigated materials, hydrothermally synthesized ZnO doped with 2 mol % Ho exhibited the highest tribocatalytic activity, achieving 96.91% degradation of paracetamol at an initial concentration of 15 mg/L within 24 h. The enhanced performance was attributed to improved charge separation induced by Ho modification, combined with the favorable rod-like morphology of the particles. Higher degradation efficiencies were observed in distilled water compared to tap and mineral water, indicating the important role of dissolved ions during the tribocatalytic process. These findings demonstrate that the synthesis route, Ho doping, and water composition collectively govern the tribocatalytic performance of ZnO-based materials, highlighting their potential for water purification.