Preparation of multi-walled carbon nanotubes based magnetic multi-template molecularly imprinted polymer for the adsorption of phthalate esters in water samples

Taking the advantages of surface imprinting, multi-template imprinting and magnetic separation, a novel magnetic multi-template molecularly imprinted polymer (mag-MMIP@MWCNTs) was prepared by using MWCNTs as support material, Fe₃O₄ as magnetic core, and dimethyl phthalate (DMP), diethyl phthalate (DEP), and dibutyl phthalate (DBP) as template molecules. This composite was characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), and the Brunauer-Emmett-Teller (BET) analysis, and was used for the simultaneous adsorption of DMP, DEP, and DBP in aqueous solution. The effects of solution pH, contact time, PAEs initial concentration, temperature, adsorption selectivity, and reusability were investigated and discussed in detail. The results demonstrated that mag-MMIP@MWCNTs exhibited fast kinetics, good magnetic separation, and excellent selectivity for the adsorption of three phthalate esters (PAEs). The adsorption kinetics followed pseudo second-order kinetic model and the adsorption thermodynamics followed Langmuir isothermal model very well, and the maximum adsorption capacities (Qₘₐₓ) of DMP, DEP, and DBP were obtained as 0.95, 1.38, and 7.09 mg g⁻¹, respectively. The Scatchard analysis revealed that the template-polymer system had a two-site binding behavior. The adsorption thermodynamic studies indicated that the adsorption processes were exothermic and spontaneous, and dominated by physical adsorption relying on hydrogen bond, hydrophobic interaction, and van der Waals force. Mag-MMIP@MWCNTs also showed good reproducibility and reusability for simultaneous adsorption of the three PAEs. The potential application of mag-MMIP@MWCNTs was proved by the removal of DMP, DEP, and DBP spiked in environmental water samples.