Preferential and Enhanced Adsorption of Methyl Green on Different Greenly Synthesized Magnetite Nanoparticles: Investigation of the Influence of the Mediating Plant Extract's Acidity.

Four magnetite nanoparticle (NP) samples have been greenly synthesized using four aqueous plant extracts, which are Artemisia herba-alba (L), Rosmarinus officinalis (L), Matricaria pubescens (L), and Juniperus phoenicia (L). The pH of these extracts are acidic (5.25, 5.05, 4.63, and 3.69, respectively). The synthesized samples were characterized by XRD, SEM, ATR-FTIR, and UV-Vis. This work aimed to study the preferential and enhanced adsorption of methyl green (MG) on the four greenly synthesized Fe3O4 surfaces by coupling three processes: MG adsorption in ambient dark conditions as the first process, followed by the thermocatalysis of the MG/Fe3O4 residual solution in the second process, and finally photocatalysis by the UV irradiation of MG/Fe3O4 residual solution after carrying out thermocatalysis. The novelty of this study lies in highlighting the influence of the mediating plant extract's acidity on the magnetite NPs' physicochemical characteristics, which impact the preferential and enhanced MG adsorption. The studied physicochemical characteristics are the functional hydroxyl group density on the magnetite surface, grain size, and band gap energy. It was found that the plant extract's acidity has a clear effect on the studied physicochemical properties. The analysis of the FTIR spectra showed that the hydroxyl group densities differ on the four magnetite samples. Furthermore, the calculated grain sizes of the magnetite samples based on XRD spectra data vary from 29.27 to 41.49 nm. The analysis of the UV-Vis spectra of the four magnetite samples showed that the estimated direct band gap energies vary from 2.87 to 2.97 eV. The obtained results showed that the decrease of the mediating plant extract's acidity leads to an increase in the hydroxyl group density on magnetite surfaces, which resulted in an increase in the MG adsorption capacities and yields in the first process of adsorption. Thus, MG adsorption was more preferred on greenly synthesized magnetite surfaces mediated by plant extracts with low acidity (Artemisia herba-alba (L) and Rosmarinus officinalis (L)). Furthermore, the increase of the plant extract's acidity leads to a decrease in the particle size and an increase in the band gap energy and, therefore, to the decrease of the electron/hole pair recombination speed upon electron excitation. So, magnetite greenly synthesized from a more acidic mediating plant extract showed higher thermo- and photocatalytic activities for MG adsorption (Juniperus phoenicia (L) and Matricaria pubescens (L)). However, under photocatalysis, the enhancement is even more significant compared to thermocatalysis.