Project description:Extraction of uranium from seawater is critical for the sustainable development of nuclear energy. However, the currently available uranium adsorbents are hampered by co-existing metal ion interference. DNAzymes exhibit high selectivity to specific metal ions, yet there is no DNA-based adsorbent for extraction of soluble minerals from seawater. Herein, the uranyl-binding DNA strand from the DNAzyme is polymerized into DNA-based uranium extraction hydrogel (DNA-UEH) that exhibits a high uranium adsorption capacity of 6.06 mg g-1 with 18.95 times high selectivity for uranium against vanadium in natural seawater. The uranium is found to be bound by oxygen atoms from the phosphate groups and the carbonyl groups, which formed the specific nano-pocket that empowers DNA-UEH with high selectivity and high binding affinity. This study both provides an adsorbent for uranium extraction from seawater and broadens the application of DNA for being used in recovery of high-value soluble minerals from seawater.
Project description:The molecule of glutaroimidedioxime, a cyclic imidedioxime moiety that can form during the synthesis of the poly(amidoxime)sorbent and is reputedly responsible for the extraction of uranium from seawater. Complexation of manganese (II) with glutarimidedioxime in aqueous solutions was investigated with potentiometry, calorimetry, ESI-mass spectrometry, electrochemical measurements and quantum chemical calculations. Results show that complexation reactions of manganese with glutarimidedioxime are both enthalpy and entropy driven processes, implying that the sorption of manganese on the glutarimidedioxime-functionalized sorbent would be enhanced at higher temperatures. Complex formation of manganese with glutarimidedioxime can assist redox of Mn(II/III). There are about ~15% of equilibrium manganese complex with the ligand in seawater pH(8.3), indicating that manganese could compete to some degree with uranium for sorption sites.
Project description:The extraction of uranium from seawater, which is an abundant resource, has attracted considerable attention as a viable form of energy-resource acquisition. The two critical factors for boosting the chemical thermodynamics of uranium extraction from seawater are the availability of sufficient amounts of uranyl ions for supply to adsorbents and increased interaction temperatures. However, current approaches only rely on the free diffusion of uranyl ions from seawater to the functional groups within adsorbents, which largely limits the uranium extraction capacity. Herein, inspired by the mechanism of plant transpiration, a plant-mimetic directional-channel poly(amidoxime) (DC-PAO) hydrogel is designed to enhance the uranium extraction efficiency via the active pumping of uranyl ions into the adsorbent. Compared with the original PAO hydrogel without plant-mimetic transpiration, the uranium extraction capacity of the DC-PAO hydrogel increases by 79.33% in natural seawater and affords the fastest reported uranium extraction average rate of 0.917 mg g-1 d-1 among the most state-of-the-art amidoxime group-based adsorbents, along with a high adsorption capacity of 6.42 mg g-1 within 7 d. The results indicate that the proposed method can enhance the efficiency of solar-transpiration-based uranium extraction from seawater, particularly in terms of reducing costs and saving processing time.
Project description:The uranium level in seawater is ?1000 times as high as terrestrial ores and can provide potential near-infinite fuel for the nuclear energy industry. However, it is still a significant challenge to develop high-efficiency and low-cost adsorbents for massively extracting uranium from seawater. Herein, a simple and fast method through low-energy consumption sunlight polymerization to direct fabrication of a poly(amidoxime) (PAO) hydrogel membrane, which exhibits high uranium adsorption capacity, is reported. This PAO hydrogel owns semi-interpenetrating structure and a hydrophilic poly(acrylamide) 3D network of hydrogel which can disperse and fix PAOs well. As a result, the amidoxime groups of PAOs exhibit an outstanding uranium adsorption efficiency (718 ± 16.6 and 1279 ± 14.5 mg g-1 of m uranium/m PAO in 8 and 32 ppm uranium-spiked seawater, respectively) among reported hydrogel-based adsorbents. Most importantly, U-uptake capacity of this hydrogel can achieve 4.87 ± 0.38 mg g-1 of m uranium/m dry gel just after four weeks within natural seawater. Furthermore, this hydrogel can be massively produced through low-energy consumption and environmentally-friendly sunlight polymerization. This work will provide a high-efficiency and low-cost adsorbent for massive uranium extraction from seawater.
Project description: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.
Project description:The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.
Project description:A new type of double uranium oxo cation [O-U-O-U-O]4+ is prepared by selective oxygen-atom abstraction from macrocyclic uranyl complexes using either boranes or silanes. A significant degree of multiple U[double bond, length as m-dash]O bonding is evident throughout the U2O3 core, but either trans-,cis- or trans-,trans-OUOUO motifs can be isolated as boron- or silicon-capped oxo complexes. Further controlled deoxygenation of the borylated system is also possible.
Project description:Spatially resolved analysis of uranium (U) isotopes in small volumes of actinide-bearing materials is critical for a variety of technical disciplines, including earth and planetary sciences, environmental monitoring, bioremediation, and the nuclear fuel cycle. However, achieving subnanometer-scale spatial resolution for such isotopic analysis is currently a challenge. By using atom probe tomography-a three-dimensional nanoscale characterisation technique-we demonstrate unprecedented nanoscale mapping of U isotopic enrichment with high sensitivity across various microstructural interfaces within small volumes (~100 nm3) of depleted and low-enriched U alloyed with 10?wt% molybdenum that has different nominal enrichments of 0.20 and 19.75% 235U, respectively. We map enrichment in various morphologies of a U carbide phase, the adjacent ?-UMo matrix, and across interfaces (e.g., carbide/matrix, grain boundary). Results indicate the U carbides were formed during casting, rather than retained from either highly enriched or depleted U feedstock materials. The approach presented here can be applied to study nanoscale variations of isotopic abundances in the broad class of actinide-bearing materials, providing unique insights into their origins and thermomechanical processing routes.
Project description:An ideal porous adsorbent toward uranium with not only large adsorption capacity and high selectivity but also broad applicability even under rigorous conditions is highly desirable but still extremely scarce. In this work, a porous adsorbent, namely [NH4]+[COF-SO3 -], prepared by ammoniating a SO3H-decorated covalent organic framework (COF) enables remarkable performance for uranium extraction. Relative to the pristine SO3H-decorated COF (COF-SO3H) with uranium adsorption capacity of 360 mg g-1, the ammoniated counterpart of [NH4]+[COF-SO3 -] affords ultrahigh uranium uptake up to 851 mg g-1, creating a 2.4-fold enhancement. Such a value is the highest among all reported porous adsorbents for uranium. Most importantly, a large distribution coefficient, K d U, up to 9.8 × 106 mL g-1 is observed, implying extremely strong affinity toward uranium. Consequently, [NH4]+[COF-SO3 -] affords highly selective adsorption of uranium over a broad range of metal ions such as SU/Cs = 821, SU/Na = 277, and SU/Sr = 124, making it as effective uranium adsorbent from seawater, resulting in amazing uranium adsorption capacity of 17.8 mg g-1. Moreover, its excellent chemostability also make it an effective uranium adsorbent even under rigorous conditions (pH = 1, 8, and 3 m acidity).
Project description:Uranium is a key element in the nuclear industry, but its unintended leakage has caused health and environmental concerns. Here we report a sp2 carbon-conjugated fluorescent covalent organic framework (COF) named TFPT-BTAN-AO with excellent chemical, thermal and radiation stability is synthesized by integrating triazine-based building blocks with amidoxime-substituted linkers. TFPT-BTAN-AO shows an exceptional UO22+ adsorption capacity of 427 mg g-1 attributable to the abundant selective uranium-binding groups on the highly accessible pore walls of open 1D channels. In addition, it has an ultra-fast response time (2 s) and an ultra-low detection limit of 6.7 nM UO22+ suitable for on-site and real-time monitoring of UO22+, allowing not only extraction but also monitoring the quality of the extracted water. This study demonstrates great potential of fluorescent COFs for radionuclide detection and extraction. By rational designing target ligands, this strategy can be extended to the detection and extraction of other contaminants.