Fast Kinetic Response and Efficient Removal of Methyl Blue and Methyl Green Dyes by Functionalized Multiwall Carbon Nanotubes Powered with Iron Oxide Nanoparticles and Citrus reticulata Peel Extract

Maghemite nanoparticles (NPs) were successfully developed using phenolic-rich extracts (cyanidin) from <i>Citrus reticulata</i> peel residues. The 11 nm maghemite NPs, obtained at 3% <i>w</i>/<i>v</i> and at 353 K, presented the optimal synthesis conditions. To improve dye adsorption performance, the synergetic adsorption behavior between these 11 nm NPs and multiwall carbon nanotubes was demonstrated. Prior to the adsorption tests, the aging effect on NPs was carefully assessed using various analytical techniques, which clearly showed the magnetite-maghemite phase transition. However, this had no impact on the cyanidin coating or adsorption properties. A remarkable percentage removal of (93 ± 3)% for methylene blue and (84 ± 3)% for methylene green was achieved in short equilibrium times of 10 and 25 min, respectively, with an optimum pH value of 5.5. Reuse experiments revealed that 90% removal for both dyes was achieved between the second to seventh regeneration cycles. Organic loading during these cycles was effectively confirmed by X-ray photoelectron spectroscopy and magnetic measurements. Dye adsorption involves a two-step mechanism: (i) electrostatic adsorption by the negative surface groups of the adsorbent (isoelectric point of 5.2) and the dye cationic groups and (ii) π-π stacking interactions between the aromatic benzene rings of the dyes, the hexagonal skeleton of the multiwall carbon nanotubes, and the phenolic ring groups of the biosynthesized sample. These results suggest that the low-cost modified phenolic adsorbent can be successfully applied to dye removal from water with promising recycling properties.