Sonophotocatalytic Degradation of Malachite Green by Nanocrystalline Chitosan-Ascorbic Acid@NiFe2O4 Spinel Ferrite

Abstract

Statistics show that more than 700 thousand tons of dye are produced annually across the globe. Around 10–20% of this is used in industrial processes such as printing and dyeing, while about 50% of the dye produced is discharged into the environment without proper physicochemical treatment. Even trace amounts of dye in water can reduce oxygen solubility and have carcinogenic, mutagenic, and toxic effects on aquatic organisms. Therefore, before dye-containing wastewater is discharged into the environment, it must be properly treated. The present study investigates the green synthesis of nickel ferrite NiFe2O4 (NIFE) spinel magnetic nanoparticles (MNPs) via chemical coprecipitation of a solution of Ni2+/Fe3+ in the presence of a biopolymer blend of chitosan (CT) and ascorbic acid (AS). The magnetic nanomaterial was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy–energy dispersive X-ray analysis (SEM-EDX), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), and vibrating-sample magnetometry (VSM). The material was further explored as a catalyst for the photocatalytic degradation of malachite green (MG) under visible light irradiation coupled with ultrasonic waves. The combination of 90 min of visible solar light irradiation with 6.35 W·mL−1 ultrasonic power at pH 8 resulted in 99% of the photocatalytic efficiency of chitosan-ascorbic acid@NIFE (CTAS@NIFE) catalyst for 70 mg·L−1 MG. The quenching of the photocatalytic efficiency from 98% to 64% in the presence of isopropyl alcohol (IPA) suggested the involvement of hydroxy (•OH) radicals in the mineralization process of MG. The high regression coefficients (R2) of 0.99 for 35, 55, and 70 mg·L−1 MG indicated the sonophotocatalysis of MG by CTAS@NIFE was best defined by a pseudo first-order kinetic model. The mechanism involves the adsorption of MG on the catalyst surface in the first step and thereby mineralization of the MG by the generated hydroxyl radicals (•OH) under the influence of visible radiation coupled with 6.34 W·mL−1 ultrasonic power. In the present study the application of photodegradation process with sonochemistry results in 99% of MG mineralization without effecting the material structure unlike happens in the case adsorption process. So, the secondary pollution (generally happens in case of adsorption) can be avoided by reusing the spent material for another application instead of disposing it. Thus, the ecofriendly synthesis protocol, ease in design of experimentation like use of solar irradiation instead of electric power lamps, reusability and high efficiency of the material suggested the study to be potentially economical for industrial development at pilot scale towards wastewater remediation.