Magnetic graphene oxide for methylene blue removal: adsorption performance and comparison of regeneration methods

A series of Fe₃O₄-graphene oxide (GO) composite materials (MGOs) with abundant surface area, rich oxygen-containing functional groups, and magnetic properties were prepared in a facile coprecipitation method and then employed for the adsorptive removal of methylene blue (MB) from water. The kinetic data were better fitted in the pseudo-second-order model than in the pseudo-first-order model, and the intraparticle diffusion model revealed the two-step diffusion process including diffusion in the boundary layer and in the porous structures. The maximum adsorption amounts of MB were calculated to be 37.5-108 mg/g at 25 °C and pH 9 using the Langmuir isotherm model. Thermodynamic study showed that the adsorption process was spontaneous, with ΔH° of 23.0-49.6 kJ/mol and ΔS° of 131-249 J∙mol^-1∙K^-1. The adsorption amount of MB increased with pH in the range of 4-10. Inorganic ions including Na⁺ and Ca²⁺ suppressed the adsorption of MB, and the more pronounced impact of Ca²⁺ was ascribed to its higher valence state. The cetyltrimethylammonium bromide (CTAB) surfactant showed a stronger inhibitory effect than Ca²⁺. The adsorption mechanism was proposed to be a combination of electrostatic interactions, hydrophobic adsorption, and electron donor-acceptor interactions. Two methods were used for the regeneration of spent MGO, and the results showed that the peroxomonosulfate (PMS) oxidation method was more favorable than the acid washing method, considering the better regeneration ability and lower amount of washing water used. Finally, the reaction mechanism of PMS oxidation was analyzed based on quenching tests and in situ open circuit potential measurements, which proved that OH and ¹O₂ played dominant roles and that the fine adsorption ability of MGO promoted the reaction between them and MB.