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At least 1,099 records · Page 61

Stripping Uranium from Seawater-Loaded Sorbents with the Ionic Liquid Hydroxylammonium Acetate in Acetic Acid for Efficient Reuse

A new stripping and recovery process was developed to harvest the uranium recovered from seawater with amidoxime-functionalized polyethylene fiber sorbents and allow reuse of the sorbent without loss of capacity and without the need to recondition the sorbent before reuse. Hydroxylammonium acetate ([NH 3 OH][OAc])/aqueous acetic acid (AcOH) solutions were used as weakly acidic stripping agents and the stripped uranium as a soluble acetate was further immobilized on shrimp shells. These solutions also stripped the vanadium and other metal ions coadsorbed, which reduce capacity through competition with uranium for sorbent binding and can resist stripping even by strong acids. [NH 3 OH][OAc]/AcOH was found to allow recovery of more than 85% of the uranium although at a substantial longer time than the current 0.5 M HCl-stripping solutions, (less than 12 h vs 48-72 h, respectively); however, the use of HCl severely compromises the capacity of the sorbent in subsequent reuse (a 50% lost was observed on the third reuse of the fiber). Both [NH 3 OH][OAc] and the acetic acid were necessary to achieve high uranium recovery without sacrificing the sorbent’s capacity on reuse. Finally, the ability to reuse the sorbent without pretreatment and with minimal capacity loss could be an important step toward making the extraction of uranium from seawater energy-efficient and economically viable.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Tuning the Cation–Anion Interactions by Methylation of the Pyridinium Cation: An X-ray Photoelectron Spectroscopy Study of Picolinium Ionic Liquids

Here, X-ray photoelectron spectroscopy is used to investigate the impact of methylation on the electronic environment of pyridinium cations. Because of the electron-donating effect of the methyl group, there is a significant increase in electron density on the cationic nitrogen. The shift of the N 1s binding energy is inversely proportional to the anion basicity. The methylation position on the electronic environment of the cationic nitrogen is investigated. The N 1s binding energy follows the trend: 1-octylpyridinium > 1-octyl-3-picolinium > 1-octyl-4-picolinium > 1-octyl-2-picolinium, which is in good agreement with the cation acidity. The increase in the inductive effect subsequently weakens the cation–anion interactions through charge transfer from the anion to the cation, causing a subtle change in the electronic environment of the anion. Such an effect is noticeably reflected in the Br 3d binding energy. It shows that the Br 3d 5/2 binding energy of 1-octyl-2-picolinium bromide is 0.2 eV lower than that of 1-octylpyridinium bromide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗