Coupling ZnO with CuO for efficient organic pollutant removal

Abstract

Fabrication of heterojunction semiconductors for the photodegradation of toxic organic dyes under sunlight exposure has earned significant recognition from researchers nowadays. On that account, we have synthesized and explored a comparative photodegradation study of ZnO/CuO nanocomposite with ZnO and CuO nanoparticles. ZnO and CuO nanoparticles have been synthesized by biosynthesis methods using Ficus benghalensis leaf extract. As-synthesized ZnO and CuO nanoparticles have been further utilized for the synthesis of ZnO/CuO nanocomposite by the mortar pestle crushing/milling method. Both biosynthesis methods and mortar pestle crushing/milling methods are simple, low-cost, and environmentally friendly. Structural, optical, and morphological analysis of all the synthesized nanomaterials have been done by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), field emission scanning electron microscopy (FESEM), energy-dispersive spectroscopy (EDS), fourier transform infrared spectroscopy (FTIR), and UV-visible spectroscopy. PXRD data reveal that synthesized ZnO nanoparticles are in the hexagonal wurtzite phase, CuO nanoparticles in the monoclinic phase, and ZnO/CuO nanocomposite in the hexagonal wurtzite as well as in monoclinic phase. FE-SEM and TEM images of ZnO/CuO nanocomposite reveal the nanorod-shaped morphology along with micro-sized and nano-sized flakes. The BET analysis shows the surface areas 18.128 m²/g for ZnO nanoparticles, 16.653 m²/g for CuO nanoparticles, and 19.580 m²/g for ZnO/CuO nanocomposite, respectively. The energy band gap values of ZnO/CuO nanocomposite are obtained 3.13 eV for ZnO and 2.76 eV for CuO, respectively. The photocatalytic behaviors of all the synthesized nanomaterials are examined against aqueous dye solutions of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) under sunlight irradiation. The results reveal that the photocatalytic degradation efficiency of ZnO/CuO nanocomposite has been found higher than with ZnO and CuO nanoparticles for all the dyes. Also, all the synthesized nanomaterials indicate higher photocatalytic degradation efficiency for methylene blue dye among all three dyes. The kinetics of photodegradation of all the dye solutions has also been investigated in the presence of ZnO, CuO, and ZnO/CuO photocatalysts separately. The results exhibit that rate constant values for all the dyes are higher with ZnO/CuO nanocomposite than with ZnO and CuO nanoparticles. ZnO/CuO nanocomposite demonstrates degradation efficiency for MB dye 99.13%, for RhB 80.21%, and for MO 67.22% after 180 min of sunlight exposure. ZnO/CuO nanocomposite and ZnO and CuO nanoparticles also show the best reusability and stability up to three cycles for photocatalytic degradation of MB dyes among all the dyes. Therefore, green synthesized ZnO/CuO nanocomposite could be used as an efficient photocatalyst for the degradation of various toxic dyes. The mineralization of different dyes using ZnO/CuO nanocomposite has been examined by FTIR analysis. Furthermore, the mineralization of MB dye has been done by total organic carbon (TOC) measurements.

Keywords: Biosynthesis; Morphologies; Organic dyes; Photocatalytic degradation; ZnO/CuO nanocomposite.