Search Results (5)

Thorium is a notable candidate for resolving uranium shortage caused by the global application of nuclear power generation. Uranium extraction from seawater is another attempt to handle its source deficiency, however, vanadium is one of the main competitive elements in that process. Exploration of probes which can discriminatively detect thorium and vanadium from uranium has primary significance for their further separation and for environmental protection. Herein, N′-(2,4-dihydroxybenzylidene)-4-hydroxylphenylhydrazide, AOH, is used as sensor for Th⁴⁺ and vanadyl (VO²⁺) determination. AOH demonstrates a specific “turn-on” fluorescence selectivity towards Th⁴⁺ over f-block and other foreign metal ions, with a detection limit (LOD) of 7.19 nM in acidic solution and a binding constant of 9.97 × 10⁹ M⁻². Meanwhile, it shows a “turn-off” fluorescence response towards VO²⁺ over other metal ions at the coexistence of Th⁴⁺, with a LOD of 0.386 μM in the same media and a binding constant of 4.54 × 10⁴ M⁻¹. The recognition mechanism, based on HRMS, ¹H NMR, and FT-IR results, demonstrates that VO²⁺ causes the fluorescence quenching by replacing Th⁴⁺ to coordinate with AOH. In real water detection tests, Th⁴⁺ and VO²⁺ exhibited satisfying recoveries. These findings expand the application of sensors in nuclide pollution control. Full article

Amidoxime-functionalized hydrogels are one of most promising adsorbents for high-efficiency uranium (U) extraction from seawater, but bioadhesion on their surface seriously decreases their adsorption efficiency and largely shortens their service life. Herein, a semi-interpenetrating zwitterion–poly(amidoxime) (ZW-PAO) hydrogel was explored through introducing a PAO polymer into a poly [3-(dimethyl 4-vinylbenzyl amino) propyl sulfonate] (PDVBAP) polyzwitterionic (PZW) network via ultraviolet (UV) polymerization. Owing to the anti-polyelectrolyte effect of the PZW network, this ZW-PAO hydrogel can provide excellent super-hydrophilicity in seawater for high-efficiency U-adsorption from seawater. Furthermore, the ZW-PAO hydrogel had outstanding anti-biofouling performance for both highly enhanced U-adsorption and a relatively long working life in natural seawater. As a result, during only 25 days in seawater (without filtering bacteria), the U-uptake amount of this ZW-PAO hydrogel can reach 9.38 mg/g and its average rate can reach 0.375 mg/(g∙day), which is excellent among reported adsorbents. This work has explored a promising hydrogel for high-efficiency U-recovery from natural seawater and will inspire new strategy for U-adsorbing materials. Full article

The study of small synthetic models for the highly selective removal of uranyl ions from seawater with amidoxime-containing materials is a valuable means to enhance their recovery capacity, leading to better extractants. An important issue in such efforts is to design bifunctional ligands and study their reactions with trans-{UO₂}²⁺ in order to model the reactivity of polymeric sorbents possessing both amidoximate and another adjacent donor site on the side chains of the polymers. In this work, we present our results concerning the reactions of uranyl and pyrimidine-2-amidoxime, a ligand possessing two pyridyl nitrogens near the amidoxime group. The 1:2:2 {UO₂}²⁺/pmadH₂/external base (NaOMe, Et₃N) reaction system in MeOH/MeCN provided access to complex [UO₂(pmadH)₂(MeOH)₂] (1) in moderate yields. The structure of the complex was determined by single-crystal X-ray crystallography. The U^VI atom is in a distorted hexagonal bipyramidal environment, with the two oxo groups occupying the trans positions, as expected. The equatorial plane consists of two terminal MeOH molecules at opposite positions and two N,O pairs of two deprotonated η² oximate groups from two 1.11000 (Harris notation) pmadH⁻ ligands; the two pyridyl nitrogen atoms and the –NH₂ group remain uncoordinated. One pyridyl nitrogen of each ligand is the acceptor of one strong intramolecular H bond, with the donor being the coordinated MeOH oxygen atom. Non-classical C_aromatic-H⋯X (X=O, N) intermolecular H bonds and π–π stacking interactions stabilize the crystal structure. The complex was characterized by IR and Raman spectroscopies, and the data were interpreted in terms of the known structure of 1. The solid-state structure of the complex is not retained in DMSO, as proven via ¹H NMR and UV/Vis spectroscopic techniques as well as molar conductivity data, with the complex releasing neutral pmadH₂ molecules. The to-date known coordination chemistry of pmadH₂ is critically discussed. An attempt is also made to discuss the technological implications of this work. Full article

3D naturally derived composites consisting of calcium alginate hydrogels (CA) and oxidized biochar obtained from Luffa cylindrica (ox-LC) were synthesized and further evaluated as adsorbents for the removal of U(VI) from aqueous media. Batch-type experiments were conducted to investigate the effect of various physicochemical parameters on the adsorption performance of materials. The maximum adsorption capacity (q_max) was 1.7 mol kg⁻¹ (404.6 mg·g⁻¹) at pH 3.0 for the CA/ox-LC with a 10% wt. ox-LC content. FTIR spectroscopy indicated the formation of inner-sphere complexes between U(VI) and the surface-active moieties existing on both CA and ox-LC, while thermodynamic data revealed that the adsorption process was endothermic and entropy-driven. The experimental data obtained from the adsorption experiments were well-fitted by the Langmuir and Freundlich models. Overall, the produced composites exhibited enhanced adsorption efficiency against U(VI), demonstrating their potential use as effective adsorbents for the recovery of uranium ions from industrial effluents and seawater. Full article

Resource shortage is a major problem in our world. Nuclear energy is a green energy and because of this and its high energy density, it has been attracting more and more attention during the last few decades. Uranium is a valuable nuclear fuel used in the majority of nuclear power plants. More than one thousand times more uranium exists in the oceans, at very low concentrations, than is present in terrestrial ores. As the demand for nuclear power generation increases year-on-year, access to this reserve is of paramount importance for energy security. Water-insoluble polymeric materials functionalized with the amidoxime group are a technically feasible platform for extracting uranium, in the form of {UO₂}²⁺, from seawater, which also contains various concentrations of other competing metal ions, including vanadium (V). An in-depth understanding of the coordination modes and binding strength of the amidoxime group with uranyl and other competing ions is a key parameter for improving extraction efficiency and selectivity. Very limited information on the complexation of {UO₂}²⁺ with amidoximes was available before 2012. However, significant advances have been made during the last decade. This report reviews the solid-state coordination chemistry of the amidoxime group (alone or within ligands with other potential donor sites) with the uranyl ion, while sporadic attention on solution and theoretical studies is also given. Comparative studies with vanadium complexation are also briefly described. Eight different coordination modes of the neutral and singly deprotonated amidoxime groups have been identified in the structures of the uranyl complexes. Particular emphasis is given to describing the reactivity of the open-chain glutardiamidoxime, closed-ring glutarimidedioxime and closed-ring glutarimidoxioxime moieties, which are present as side chains on the sorbents, towards the uranyl moiety. The technological implications of some of the observed coordination modes are outlined. It is believed that X-ray crystallography of small uranyl-amidoxime molecules may help to build an understanding of the interactions of seawater uranyl with amidoxime-functionalized polymers and improve their recovery capacity and selectivity, leading to more efficient extractants. The challenges for scientists working on the structural elucidation of uranyl coordination complexes are also outlined. The review contains six sections and 95 references. Full article