More than 1000× uranium exists in the oceans than exists in terrestrial ores. With nuclear power generation expected to increase over the coming decades, access to this unconventional reserve is a matter of energy security. With origins in the mid-1950s, materials have been developed for the selective recovery of seawater uranium for more than six decades, with a renewed interest in particular since 2010. This review comprehensively surveys materials developed from 2000–2016 for recovery of seawater uranium, in particular including recent developments in inorganic materials; polymer adsorbents and related research pertaining to amidoxime; and nanostructured materials such as metal–organic frameworks, porous-organic polymers, and mesoporous carbons. Challenges of performing reliable and reproducible uranium adsorption studies are also discussed, as well as the standardization of parameters necessary to ensure valid comparisons between different adsorbents.

Materials for the Recovery of Uranium from Seawater

Chelating polymers and related supports for separation and preconcentration of trace metals.

The recovery of uranium (U) from seawater has been investigated for over six decades in efforts to secure uranium sources for future energy production. The majority of the research activities have focused on inorganic materials, chelating polymers, and nanomaterials. Previous studies of uranium adsorption from aqueous solutions, mainly seawater, are reviewed here with a focus on various adsorbent materials, adsorption parameters, adsorption characterization, and marine studies. Continuous progress has been made over several decades, with adsorbent loadings approaching 3.2 mg U/g adsorbent in equilibrium with seawater. Further research is needed to improve first, the viability including improved capacity, selectivity, and kinetics, and second, the sorbent regeneration for multicycle use. An overview of the status of the uranium adsorption technology is provided and future research needs to make this technology commercially competitive are discussed.

Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs

In total there is hundreds of times more uranium in sea water than on land, but extracting it for use in nuclear power generation is challenging due to its low concentration (∼3 ppb) and the high salinity background. Current approaches based on sorbent materials are limited due to their surface-based physicochemical adsorption nature. Here we use a half-wave rectified alternating current electrochemical (HW-ACE) method for uranium extraction from sea water based on an amidoxime-functionalized carbon electrode. The amidoxime functionalization enables surface specific binding to uranyl ions, while the electric field can migrate the ions to the electrode and induce electrodeposition of uranium compounds, forming charge-neutral species. Extraction is not limited by the electrode surface area, and the alternating manner of the applied voltage prevents unwanted cations from blocking the active sites and avoids water splitting. The HW-ACE method achieved a ninefold higher uranium extraction capacity (1,932 mg g−1) without saturation and fourfold faster kinetics than conventional physicochemical methods using uranium-spiked sea water. The large amount of uranium in the oceans could be exploited for nuclear fuel, but existing physicochemical extraction methods are limited in terms of capacity and rates of removal. Here the authors use an electrochemical extraction technique, demonstrating improved uptake capacity and kinetics.

A half-wave rectified alternating current electrochemical method for uranium extraction from seawater

Nature can efficiently recognize specific ions by exerting second-sphere interactions onto well-folded protein scaffolds. However, a considerable challenge remains to artificially manipulate such affinity, while being cost-effective in managing immense amounts of water samples. Here, we propose an effective approach to regulate uranyl capture performance by creating bio-inspired nano-traps, illustrated by constructing chelating moieties into porous frameworks, where the binding motif’s coordinative interaction towards uranyl is enhanced by introducing an assistant group, reminiscent of biological systems. Representatively, the porous framework bearing 2-aminobenzamidoxime is exceptional in sequestering high uranium concentrations with sufficient capacities (530 mg g−1) and trace quantities, including uranium in real seawater (4.36 mg g−1, triple the benchmark). Using a combination of spectroscopic, crystallographic, and theory calculation studies, it is revealed that the amino substituent assists in lowering the charge on uranyl in the complex and serves as a hydrogen bond acceptor, boosting the overall uranyl affinity of amidoxime. Uranium extraction is important for both uranium recovery and nuclear waste management. Here, inspired by the high sensitivity of proteins towards specific metal ions, Ma and colleagues demonstrate that introducing secondary coordination spheres into amidoxime-functionalized porous polymers can enhance their uranyl chelating abilities.

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Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste

Hydroxylamine derivatives of cross-linked poly(acrylonitriles), so-called poly(acrylamidoxime) resins, are suitable for the accumulation of uranium from natural seawater of pH = 8.1–8.3. Depending on the method of manufacture, these sorbers yield excellent uranium loadings up to some thousand ppm which roughly equals the average uranium content of actually explored uranium ores. The rate of uranium uptake, which is 5-30 ppm/d at room temperature, increases with increasing temperature of seawater. Uranium can be eluted by 1 M HCl with an elution efficiency of more than 90%. Owing to a certain instability of the uranium binding groups in acid eluants, the uranium uptake decreases with increasing number of sorption-elution cycles. Hydroxylamine derivatives of poly(acrylonitrile) are shown to contain simultaneously at least two kinds of functional groups: open-chain amidoxime groups which are stable and cyclic imidoxime groups which are unstable in 1 M HCl. Experimental evidence is presented that the...

Development of Sorbers for the Recovery of Uranium from Seawater. Part 2. The Accumulation of Uranium from Seawater by Resins Containing Amidoxime and Imidoxime Functional Groups

At an average uranium content of 3.3 ppb the oceans can be considered as a very low-grade but practically unlimited source of uranium. Some essential chemical aspects of a large-scale sorptive recovery of uranium from seawater are discussed with special emphasis on required sorber properties such as high physical and chemical stability in seawater, fast and selective uptake of uranium, as well as a sufficient loading capacity. Systematic screening tests, including about 200 sorber materials on the basis of organic ion-exchange resins, identified cross-linked poly(acrylamidoximes) as the most promising candidate sorbers. Their uranium uptake closely approaches the uranium content of actually explored uranium ores.

Ludwig Astheimer

Papers

Development of Sorbers for the Recovery of Uranium from Seawater. Part 2. The Accumulation of Uranium from Seawater by Resins Containing Amidoxime and Imidoxime Functional Groups

Development of Sorbers for the Recovery of Uranium from Seawater. 1. Assessment of Key Parameters and Screening Studies of Sorber Materials

Tetraoxotechnetat(VI) und ‐rhenat(VI)

Preparation and Properties of Tetraoxotechnetate (VI) and Tetraoxorhenate (VI)

Tetraoxotechnetat(vi) und -rhenat(vi)