Yolk–shell microspheres assembled from Preyssler‐type NaP5W30O11014− polyoxometalate and MIL‐101(Cr) metal–organic framework: A new inorganic–organic nanohybrid for fast and selective removal of cationic organic dyes from aqueous media

Novel inorganic–organic yolk–shell microspheres based on Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate and MIL‐101(Cr) metal–organic framework (P₅W₃₀/MIL‐101(Cr)) were synthesized by reaction of K_12.5Na_1.5NaP₅W₃₀O₁₁₀], Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions at 200°C for 24 h. The as‐prepared yolk–shell microspheres were fully characterized using various techniques. All analyses confirmed the incorporation of the Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate into the three‐dimensional porous MIL‐101(Cr) metal–organic framework. The results revealed that P₅W₃₀/MIL‐101(Cr) demonstrated rapid adsorption of cationic methylene blue (MB) and rhodamine B (RhB) with ultrahigh efficiency and capacity, as well as achieving rapid and highly selective adsorption of MB from MB/MO (MO = methyl orange), MB/RhB and MB/RhB/MO mixtures. The P₅W₃₀/MIL‐101(Cr) adsorbent not only exhibited a high adsorption capacity of 212 mg g^?1, but also could quickly remove 100% of MB from a dye solution of 50 mg l^?1 within 8 min. The effects of some key parameters such as adsorbent dosage, initial dye concentration and initial pH on dye adsorption were investigated in detail. The equilibrium adsorption data were better fitted by the Langmuir isotherm. The adsorption kinetics was well modelled using a pseudo‐second‐order model. Also, the inorganic–organic hybrid yolk–shell microspheres could be easily separated from the reaction system and reused up to four times without any change in structure or adsorption ability. The stability and robustness of the adsorbent were confirmed using various techniques.