Novel polyvinyl alcohol-assisted MnO2–ZnO–CuO nanocomposites as an efficient photocatalyst for methylene blue degradation from wastewater

Abstract

Pristine ZnO (Z), MnO₂ (M), CuO (C) photocatalysts and polyvinyl alcohol (PVA)-assisted MnO₂–ZnO–CuO (MZC) nanocomposites were synthesized via the sol–gel method. The synthesized samples were characterized using thermal analysis (TGA), X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscopy (SEM), energy dispersive X-ray (EDS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The thermal analysis results of the prepared nanomaterial confirmed that the suitable calcination temperature for the synthesis of these nanomaterials is 420 °C. In addition to the morphological and elemental composition, the characteristic diffraction peaks of the MZC nanomaterial were found to align with those of the pristine Z, M, and C photocatalysts. The photocatalytic activities of the synthesized nanomaterials for methylene blue (MB) degradation were evaluated under optimized conditions. The degradation efficiencies of Z, M, C, and MZC were found to be 45%, 57%, 66%, and 93%, respectively, for MB in 180 minutes. The MZC nanocomposite exhibited superior photocatalytic activity compared to the pristine materials, which is attributed to the synergetic effect of the Z, M, and C photocatalysts. The effects of pH, initial dye concentration, and catalyst load were also explored to determine the optimum conditions. The best photocatalytic efficiency was observed at pH 8, with a 130 mg L⁻¹ catalyst load, and a 10 mg L⁻¹ initial dye concentration. The efficiency of the MZC nanocomposite in real textile wastewater was also tested, achieving 80% degradation of pollutants within 180 minutes. Recycling experiments were conducted for four consecutive cycles under optimal conditions. The photodegradation efficiency for the first, second, third, and fourth cycles was 93%, 91%, 90%, and 89%, respectively, demonstrating high consistency in photodegradation performance across the four cycles. Moreover, a Z-scheme photocatalytic mechanism was proposed as a potential mechanism for the MZC photocatalytic system.