Highly efficient functionalized MOF-LIC-1 for Extraction of U(VI) and Th(IV) from Aqueous Solution: Experimental and Theoretical Studies

A set of four new functionalized MOFs, namely MOF-LIC-DPPC, MOF-LIC-GA, MOF-LIC-PCA and MOF-LIC-SA, were synthesized via the post-synthetic modification (PSM) strategy using MOF-LIC-1 for efficient extraction of U(VI) and Th(IV) from an aqueous medium. FTIR, powder XRD, TGA and SEM-EDX were employed for characterization of the functionalized MOFs. Sorption studies for U(VI) and Th(IV) were performed by monitoring the pH and contact time. Interestingly, the modified MOF-LIC-SA displayed rapid (∼5 min) and efficient extraction towards U(VI) and Th(IV) from an aqueous medium and modified MOF-LIC-DPPC displayed enhanced thermal stability (600 °C) compared with the parent MOF-LIC-1 (450 °C). These studies revealed that the grafted functionalities on MOF-LIC-1 possess enhanced sorption efficiency towards U(VI) and Th(IV) as well as thermal stability. MOF-LIC-SA exhibited the highest sorption capacity towards U(VI) and Th(IV), viz. 298 mg g-1 (pH 6) and 149 mg g-1 (pH 6), respectively. Leaching, recyclability, and radiation stability studies were also performed using MOF-LIC-1 MOFs. Additionally, we investigated the nature of U(VI) interactions on MOFs by applying density functional theory (DFT). PSM MOFs with various functionalities display high selectivity and efficient extraction of U(VI) and Th(IV) over a wide pH range (2-9) and also exhibit easy recovery of metal ions from MOFs. These studies reveal that U(VI) and Th(IV) can be extracted from aqueous streams in a pH range from 6 to 8 and potential applications of these MOFs include recovery of U(VI) and Th(IV) from mine water, sea water, etc. The studies reported in the present work also have extensive potential applications for environmental concerns as well as in the nuclear industry.