Strategies toward the Synthesis of Advanced Functional Sorbent Performance for Uranium Uptake from Seawater

A polymer fiber-based adsorbent (AF1) composed of acrylonitrile and itaconic acid functional groups was synthesized by a radiation-induced graft polymerization technique onto hollow-gear shaped polyethylene (PE) fibers. Investigation of the optimum reaction parameters for the conversion of grafted cyano moieties into amidoxime groups was conducted by the reaction with hydroxylamine at different temperatures and periods in a variety of aqueous and organic solvents. The 13C CP/MAS spectra of amidoximated AF1 adsorbent fibers from water–methanol and dimethyl sulfoxide (DMSO) revealed that both the cyclic imide dioxime and open-chain amidoxime were formed through the reaction. The conversion from amidoxime to imide dioxime was found to occur slowly and gradually with the increasing reaction time. The quicker diffusion of DMSO as compared to that of water–methanol, in the grafted trunk PE fiber, resulted in faster kinetics of the amidoximation reaction. The uranium adsorption capacity of the amidoximated AF1 samples was determined after (i) 24 h contact with sodium-based brine spiked with uranium and (ii) 56 days of exposure to filtered seawater (Sequim Bay, WA, USA) in flow-through columns. The uranium extraction performance of the adsorbents after exposure to filtered seawater was consistent with the laboratory screening results, and the amidoximated AF1 samples (in DMSO at 70 °C for 3 h) exhibited the highest 56 day uranium adsorption capacity (5.04 ± 0.15 g U/kg-ads) with faster adsorption kinetics compared to the pristine AF1 adsorbents.