An organic-inorganic hybrid nanomaterial composed of a Dowson-type (NH 4 ) 6 P 2 Mo 18 O 62 heteropolyanion and a metal-organic framework: synthesis, characterization, and application as an effective adsorbent for the removal of organic dyes.

In this work, an inorganic-organic hybrid nanomaterial, P 2 Mo 18 /MIL-101(Cr), based on Wells-Dawson-type (NH 4 ) 6 P 2 Mo 18 O 62 polyoxometalate (abbreviated as P 2 Mo 18 ) and the MIL-101(Cr) metal-organic framework was fabricated by the reaction of (NH 4 ) 6 P 2 Mo 18 O 62 , Cr(NO 3 ) 3 ·9H 2 O 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 P 2 Mo 18 O 62 6- 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 m 2 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.