Post synthetically modified IRMOF-3 for efficient recovery and selective sensing of U(vi) from aqueous medium

Abstract

A simple and efficient route to develop various novel functionalized MOF materials for rapid and excellent recovery of U(VI) from aqueous medium, along with selective sensing has been demonstrated in the present study. In this connection, a set of four distinct post synthetically modified (PSM) iso-reticular metal organic frameworks were synthesized from IRMOF-3 namely, IRMOF-PC (2-pyridine carboxaldehyde), IRMOF-GA (glutaric anhydride), IRMOF-SMA (sulfamic acid), and IRMOF-DPC (diphenylphosphonic chloride) for the recovery and sensing of U(VI) from aqueous medium. The MOFs were characterized by Fourier transform infrared spectroscopy (FTIR), powder XRD, BET surface area analysis, thermogravimetric analysis (TGA), NMR (¹³C, ¹H and ³¹P), Scanning Electron Microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). Among all MOFs, post synthetically modified IRMOF-SMA showed enhanced thermal stability of about 420 °C. The MOFs were investigated for U(VI) sorption studies using a batch technique. All the MOFs exhibit excellent sorption capacity towards U(VI) (>90%) and maximum uptake was observed at pH 6. Sorption capacity of MOFs have the following order; IRMOF-3-DPC (300 mg U g⁻¹) > IRMOF-SMA (292 mg U g⁻¹) > IRMOF-PC (289 mg U g⁻¹) > IRMOF-GA (280 mg U g⁻¹) > IRMOF-3 (273 mg U g⁻¹). IRMOF-DPC shows rapid sorption of uranium within 5 min with excellent uptake of U(VI) (>99%). The desorption of U(VI) was examined with different eluents and 0.01 M HNO₃ was found to be most effective. The fluorescence sensing studies of U(VI) via IRMOF-3 and its PSM MOFs revealed high sensitivity and selectivity towards U(VI) over other competing rare earth metal ions (La³⁺, Ce⁴⁺, Sm³⁺, Nd³⁺, Gd³⁺, and Eu³⁺), wherein IRMOF-GA displayed an impressive detection limit of 0.36 mg L⁻¹ for U(VI).