Synthesis of pH responsive malononitrile functionalized metal organic framework MIL-100(Fe) for efficient adsorption of uranium U(VI) from real-life alkaline leach liquor

Abstract

The porous framework of MIL-100(Fe) was functionalized using malononitrile (MN), through an in-situ Knoevenagel condensation reaction to introduce abundant –C≡N groups on the surface of the developed adsorbent. The resultant MN-functionalized MIL-100(Fe) exhibited excellent Uranium (U(VI)) removal capacity (i.e., 270 mg/g) at highly alkaline pH (⁓ 10). Different coexisting cations and anions show negligible influence on the U-removal and it was 92.1–99.7 % in presence of different co-ions, with the concentration from 10 to 50 mg/L. Moreover, MIL-100(Fe)_MN showed extremely selective U removal from the actual alkaline leach liquor (⁓ 97 %), without any pH adjustment and leaching of the constituent Fe. The surface-grafted –C≡N groups were predominantly active towards the coordinative interactions with the U(VI) ionic moieties, as evident from the XPS and FTIR analysis. The MIL-100(Fe)_MN adsorbent was also subjected to five consecutive adsorption-desorption cycles, with >90 % U removal after 5th cycle. Moreover, the regenerated MIL-100(Fe)_MN was structurally and functionally resilient, as observed from the morphological and crystallographic analysis. A convection-pore diffusion based transport model was used to analyze the optimized mass transfer parameters. Overall, the present study highlights the simple design and development of malononitrile-functionalized MIL-100(Fe) as an efficient and selective adsorbent for U(VI) removal from U-rich alkaline leach liquor.