An organic–inorganic hybrid nanomaterial composed of a Dowson-type (NH4)6P2Mo18O62 heteropolyanion and a metal–organic framework: synthesis, characterization, and application as an effective adsorbent for the removal of organic dyes

Abstract

In this work, an inorganic–organic hybrid nanomaterial, P₂Mo₁₈/MIL-101(Cr), based on Wells–Dawson-type (NH₄)₆P₂Mo₁₈O₆₂ polyoxometalate (abbreviated as P₂Mo₁₈) and the MIL-101(Cr) metal–organic framework was fabricated by the reaction of (NH₄)₆P₂Mo₁₈O₆₂, Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions. The as-prepared recyclable nanohybrid was fully characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) equipped with energy dispersive X-ray microanalysis (EDX), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy and Brunauer–Emmett–Teller (BET) specific surface area studies. All the analyses confirmed the successful insertion of P₂Mo₁₈O₆₂⁶⁻ heteropolyanion within the cavities of MIL-101(Cr). The encapsulated MIL-101(Cr) showed a considerable decrease in both pore volume and surface area compared with MIL-101(Cr) due to incorporation of the very large Dowson-type polyoxometalate into the three-dimensional porous MIL-101(Cr). The nanohybrid had a specific surface area of 800.42 m² g⁻¹. The adsorption efficiency of this nanohybrid for removal of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) from aqueous solutions was evaluated. Surprisingly, the composite not only presented a high adsorption capacity of 312.5 mg g⁻¹ for MB, but also has the ability to rapidly remove 100% MB from a dye solution of 50 mg L⁻¹ within 3 min. These results confirmed that this adsorbent is applicable in a wide pH range of 2–10. The nanohybrid showed rapid and selective adsorption for cationic MB and RhB dyes from MB/MO, MB/RhB, MO/RhB and MB/MO/RhB mixed dye solutions. The equilibrium adsorption data were better fitted by the Langmuir isotherm. Kinetics data indicate that the adsorption of the dye follows a pseudo-second order kinetics model. Also, this material could be effortlessly separated and recycled without any structural modification. Accordingly, it is an efficient adsorbent for removing cationic dyes.