Abstract

This study aims to investigate the photocatalytic degradation performance, mechanism, and dynamics of methyl orange (MO) which is a widely used organic dye in textile industries as well a hazardous wastewater pollutant. The degradation process was catalyzed by employing a synthesized Fe3O4 magnetic nanoparticle (NP) using the coprecipitation method. The structural and morphological properties of the synthesized Fe3O4 NPs were investigated by employing XRD, HR-SEM, and XPS, which proved that acquired Fe3O4 NPs were in a pure phase. Moreover, the crystallite sizes fall in the range of 28–31.8 nm and were estimated by applying the Scherrer equation on the XRD spectrum as well as calculated independently by applying a statistical approach on the SEM micrographs. The UV–Vis maximum in the visible range at 468.8 nm consists of two absorption frequency bands due to the effect of the hydrogen-bond interaction between water and the azo nitrogens in the MO. A non-monotonic spectral dynamic accompanied by peak wavelength shifts, as well as the absolute signal amplitude and signal area of the MO band, suggests that a cleavage of the azo bond is not the only and/or the dominant process in the photocatalytic oxidization of the MO in a protic solvent. The overall absorbance process is a complicated response to a combination of nonspecific and specific solute-solvent interactions, dipole-dipole interactions, hydrogen-bonding networks, and other possible intermolecular interactions such as hydrophobic/hydrophilic interactions. A bi-exponential decay was found to be the best fitting function to model the decay of the time-dependent electrical conductivity of the MO aqueous solution under photocatalytic oxidization. The Fe3O4 NPs exhibited a 98.3% removal of MO within 110 min. Photocatalytic degradation of methyl orange can be modeled to the first-order model with a rate constant k of 0.037 min−1 taking into account the initial concentration of 1175 ppm of MO. The degradation/decolorization efficiency deduced from the low-frequency band of the visible spectra is around 99.4% after 110 min. The real-time degradation/decolorization efficiencies deduced from the overall absorbance maxima and the low-frequency band have a discrepancy of 50.1% at 20 min and 12.3% at 60 min representing the progressive attenuation of the H-bond impact dissociation of MO (degradation/decolorization).

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