Preparation and characterization of novel polyoxometalate/CoFe2O4/metal–organic framework magnetic core–shell nanocomposites for the rapid removal of organic dyes from water

Abstract

In this study, the MIL-101(Cr) metal–organic framework was functionalized with a Dowson-type polyoxometalate (P₂W₁₈O₆₂⁶⁻; POM) and magnetic spinel cobalt ferrite (CoFe₂O₄; CFO) through a hydrothermal route and was characterized by means of FT-IR, XRD, FE-SEM, EDX, BET, and VSM measurements. All analyses confirmed the successful encapsulation of POM (∼32.2 wt%) into the magnetic MIL-101(Cr) framework. Compared to the pristine MIL-101(Cr) MOF, the as-prepared magnetic ternary nanocomposite (abbreviated as POM/CFO/MIL-101(Cr)) demonstrated a notable decrease in both the surface area and pore volume because of the incorporation of CoFe₂O₄ nanoparticles and huge P₂W₁₈O₆₂⁶⁻ polyanions into the cages of the MIL-101(Cr) framework. The POM/CFO/MIL-101(Cr) was then applied as a magnetically separable adsorbent for the rapid elimination of rhodamine B (RhB), methyl orange (MO), and methylene blue (MB) dye pollutants from aqueous solutions. For achieving the optimized conditions, the effects of initial pH, initial dye concentration, temperature, salt effect, and adsorbent dose on MB and RhB elimination were investigated. The dye adsorption isotherms followed the Langmuir model and pseudo-second-order kinetic model. The POM/CFO/MIL-101(Cr) composite material not only exhibited a fast adsorption rate towards dye molecules, but also demonstrated the selective adsorption of the cationic dyes in wastewater. The recycling experiments also demonstrated that the POM/CFO/MIL-101(Cr) adsorbent was highly stable and could be quickly recovered under a magnetic field without any alteration in the structure. The high adsorption capacity, simple fabrication method, rapid separation by a magnet and supreme reusability of the POM/CFO/MIL-101(Cr) nanocomposite make it an attractive adsorbent for the elimination of cationic dyes from wastewater.