β-Diketone-Driven Deep Eutectic Solvent for Ultra-Efficient Natural Stable Lithium-7 Isotope Separation

Abstract

6Li and 7Li are strategic resources. Because Li+ ions have no outermost electrons and the radii of 6Li and 7Li differ by only one neutron, the separation of the naturally stable isotopes of Li, especially by solvent extraction, is recognized as a difficult problem worldwide. Therefore, in this paper, an advanced β-diketone-driven deep eutectic solvent (DES) extraction system containing 2-thenoyltrifluoroacetone (HTTA) and tri-n-octyl phosphine oxide (TOPO) is introduced to the extraction and separation of 6Li+ and 7Li+ ions. Compared with those of reported HTTA extraction systems and crown ether extraction systems, the separation coefficient (β7Li/6Li) of the β-diketone-driven DES extraction system can reach the best value of 1.068, which is now the highest known β-value reported in the extraction system. From the intramolecular hydrogen bond of HTTA to the intermolecular hydrogen bond of DES, the bond energy increases by 47.8%. Because the active site of the proton in DES provides a higher energy barrier for the separation of 7Li, the β7Li/6Li is significantly increased. The extractions were characterized by spectrum, using 1H nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The mechanism was determined on the basis of the reaction kinetics and density functional theory (DFT). The DES extractant shows excellent cycle performance with regard to stripping and reusability. In conclusion, the highly efficient, economical, and stable β-diketone-driven DES extraction system can be used for the separation of naturally stable Li isotopes, which provides good industrial application prospects.