Novel green strategy for CuO–ZnO–C nanocomposites fabrication using marigold (Tagetes spp.) flower petals extract with and without CTAB treatment for adsorption of Cr(VI) and Congo red dye

Abstract

The CuO–ZnO-Carbon (CZC) nanocomposites (NCs) were synthesized via a green method at 300 and 400 °C calcinated temperatures, using waste marigold (Tagetes spp.) flower petal extract as a reducing agent and carbon source. A novel green strategy for the synthesis of highly effective CZC NCs was developed which showed better adsorption of toxic Cr(VI) and Congo red (CR) dye compared to unsupported carbon NCs. In this strategy, fine powder of petals as carbon source were passed with the flower liquid extract during the filtration process, which supported the metal oxides nanorods(NRs)/nanoparticles(NPs) on the surface. Furthermore, the surface of the synthesized NCs was modified by Cetyl Trimethyl Ammonium Bromide (CTAB) cationic surfactant to increase surface functionality, surface area, and positive charge density of NCs. Additionally, the adsorption performance of Cr(VI) and CR dye improved from acidic pH to neutral pH after surfactant modification of NCs compared to unmodified NCs. The characterization techniques such as Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) surface area analysis, Point of zero charge (pHpzc), Field Emission Scanning Electron Microscopy (FE-SEM), Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were performed to examine physio-chemical properties of NCs and CTAB modified NCs. The FTIR and BET analysis confirmed that CTAB modified NCs showed excellent functionality and more than 49% and ~67% greater surface area than CZC-300 and CZC-400, respectively, which prepared at 300 and 400 °C temperature. XRD analysis confirmed that NCs were highly crystalline and no phase change after surfactant modification. The FE-SEM and TEM analysis confirmed the pentagonal NRs and spherical NPs of ZnO and CuO, respectively, were formed on the carbon surface. After CTAB modification, no change in the surface morphology of NCs was observed. Thus, comparative study of NCs and CTAB modified NCs was done for Cr(VI) and CR dye adsorption by varying batch conditions, such as initial pH, contact time, temperature, and initial concentration of Cr(VI)/CR dye. The equilibrium time and concentration data were fitted with non-linear forms of kinetic and isotherm models, respectively. CTAB modified CZC-300 NCs showed excellent adsorption capacity for both pollutants up to pH 6 compared to CZC-300 and CZC-400 NCs. Additionally, the maximum adsorption capacity of CTAB modified NCs for Cr(VI) and CR dye were 201.56 and 331.36 mg/g, respectively, at pH 2 and 30 °C and increased with increasing temperature. The effect of co-existing anions on adsorption capacity of both NCs for Cr(VI) and CR dye adsorption was investigated. The regeneration and reusability experiments of both NCs were also performed.