Synthesis of polyethylenimine-functionalized poly(glycidyl methacrylate) magnetic microspheres and their excellent Cr(VI) ion removal properties

• The PEI-grafted magnetic polymer microspheres were prepared.
• The adsorbent is micro-sized and monodispersed.
• The adsorbent has a much higher adsorption capacity than others reported.
• The adsorption rate is considerably fast.
• The adsorbent has a good reusability.

Micron-sized polyethylenimine-functionalized poly(glycidyl methacrylate) superparamagnetic microspheres (m-PGMA-PEI) were prepared by a process involving: (1) synthesis of PGMA microspheres using the dispersion polymerization method; (2) ring-opening reaction of epoxy groups on PGMA microspheres with ethylenediamine (EDA) to yield amino groups; (3) in situ coprecipitation of Fe3O4 nanoparticles into the pores of microspheres; (4) Michael addition of amino groups with methyl acrylate (MA) to yield ester groups; and (5) amidation of the terminal ester groups with polyethylenimine (PEI). Once generated, the resulting m-PGMA-PEI microspheres were tested for their ability to remove Cr(VI) from an aqueous solution in batch experiments. The results demonstrated that Cr(VI) adsorption was significantly pH dependent. The optimized pH value was 2.0. The adsorption isotherm of the adsorbent fit the Langmuir model, with the maximum adsorption capacity of 492.61 mg/g. The Cr(VI) adsorption rate was rapid, and the adsorption reached equilibrium within 15 min. The thermodynamic parameters (ΔG0, ΔH0, ΔS0) demonstrated that the adsorption process was endothermic and spontaneous in nature. The presence of the coexisting anions involving Cl−, NO3-, H2PO4- and HPO42- had no remarkable influence on Cr(VI) adsorption except SO42-. The regeneration study proved that the m-PGMA-PEI microspheres could be repeatedly utilized with no significant loss of adsorption efficiency.

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