Encapsulation of Uranium Oxide in Multiwall WS2 Nanotubes.

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60 °C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS2 nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO2 nanoparticles anchor within the WS2 nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS2 nanotubes, as demonstrated herein.

U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo-salt Framework.

Pentavalent uranium compounds are key components of uranium's redox chemistry and play important roles in environmental transport. Despite this, well-characterized U(V) compounds are scarce primarily because of their instability with respect to disproportionation to U(IV) and U(VI). In this work, we provide an alternate route to incorporation of U(V) into a crystalline lattice where different oxidation states of uranium can be stabilized through the incorporation of secondary cations with different sizes and charges. We show that iriginite-based crystalline layers allow for systematically replacing U(VI) with U(V) through aliovalent substitution of 2+ alkaline-earth or 3+ rare-earth cations as dopant ions under high-temperature conditions, specifically Ca(UVIO2)W4O14 and Ln(UVO2)W4O14 (Ln=Nd, Sm, Eu, Gd, Yb). Evidence for the existence of U(V) and U(VI) is supported by single-crystal X-ray diffraction, high energy resolution X-ray absorption near edge structure, X-ray photoelectron spectroscopy, and optical absorption spectroscopy. In contrast with other reported U(V) materials, the U(V) single crystals obtained using this route are relatively large (several centimeters) and easily reproducible, and thus provide a substantial improvement in the facile synthesis and stabilization of U(V).

The Role of Alkalis in Orchestrating Uranyl-Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide.

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb+ and Cs+ salts (Cs-U1 and Rb-U1). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li+, Na+ and K+ analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U1, the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO2 in the solid-state, converting to Cs4[UVIO2(CO3)3], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsUVO3, where the parent phase has been computationally predicted, but not yet synthesized.

Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me2NH2]V3O7 is predominantly upheld by the H-bond interaction between anionic framework [V3O7]nn- and intercalated [Me2NH2]+. The [Me2NH2]+ within [Me2NH2]V3O7 can be readily exchanged with UO22+. [Me2NH2]V3O7 exhibits high exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO22+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me2NH2]V3O7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me2NH2]V3O7 can also efficiently separate UO22+ from Cs+ or Sr2+ achieving the highest separation factors (SFU/Cs of 589 and SFU/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO22+ and [V3O7]nn-, whereas the ion exchange rate is influenced by the mobility of UO22+ and [Me2NH2]+. Our experimental findings indicate that [Me2NH2]V3O7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

Engineering an upconversion fluorescence sensing platform with "off-on" pattern through specific DNAzyme-mediated signal amplification for supersensitive detection of uranyl ion.

An upconversion fluorescence sensing platform was developed with upconversion nanoparticles (UCNPs) as energy donors and gold nanoparticles (AuNPs) as energy acceptors, based on the FRET principle. They were used for quantitative detection of uranyl ions (UO22+) by amplifying the signal of the hybrid chain reaction (HCR). When UO22+ are introduced, the FRET between AuNPs and UCNPs can be modulated through a HCR in the presence of high concentrations of sodium chloride. This platform provides exceptional sensitivity, with a detection limit as low as 68 pM for UO22+ recognition. We have successfully validated the reliability of this method by analyzing authentic water samples, achieving satisfactory recoveries (89.00%-112.50%) that are comparable to those of ICP-MS. These results indicate that the developed sensing platform has the capability to identify trace UO22+ in complex environmental samples.

Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy.

U(VI) peroxide phases (studtite and meta-studtite) are found throughout the nuclear fuel cycle and exist as corrosion products in high radiation fields. Peroxides are part of a family of reactive oxygen species (ROS) that include hydroperoxyl and superoxide species and are produced during alpha radiolysis of water. While U(VI) peroxides have been thoroughly investigated, the incorporation and stability of ROS species within studtite have not been validated. In the current study, electron paramagnetic resonance (EPR) spectroscopy was used to identify the presence of free radicals within a series of U(VI) peroxide samples containing depleted, highly enriched, and natural uranium. Density functional theory calculations indicated that the predicted EPR signals matched well with a superoxide (O2 -⋅) species incorporated into the studtite structure, confirming the presence of ROS in the material. Further analysis of samples that were synthesized between 1945 and 2023 indicated that there is a correlation between the radical signal and the product of specific activity multiplied by age of the sample.

Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl-Organic Hybrid Materials.

A series of compounds of the form [HAr]2 [UO2 X4 ] is reported here, wherein Ar is systematically varied between pyridine (1-X), quinoline (2-X), acridine (3-X), 2,5-dimethylpyrazine (4-X), quinoxaline (5-X), and phenazine (6-X), and X=Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr]+ cations and [UO2 Cl4 ]2- anion in the crystalline state, and of the assembly. The distinct energy transfer pathways in each compound are discussed.

Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing NpV and the Uranyl Peroxide Nanocluster U60 Ox30.

Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U60 Ox30 , [((UO2 )(O2 ))60 (C2 O4 )30 ]60- , and neptunium(V) as a function of neptunium concentration. Ultra-small and small angle X-ray scattering were used to observe these interactions in the aqueous phase, and X-ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U60 Ox30 when the neptunium concentration is≤10 mM, whereas (NpO2 )2 C2 O4 ⋅ 6H2 O(cr) and studtite ultimately form at 15-25 mM neptunium. The latter result suggests that neptunium coordinates with the bridging oxalate ligands in U60 Ox30 , leaving metastable uranyl peroxide species in solution. This is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.

Electrospray Ionization Tandem Mass Spectrometry With Collision Induced Dissociation of Uranyl Peroxide Nanoclusters Containing Various Uranyl Bridging Ligands.

Electrospray ionization tandem mass spectrometry with collision-induced dissociation (ESI-MS/MS) was utilized to study the gas phase fragmentation of uranyl peroxide nanoclusters with hydroxo, peroxo, oxalate, and pyrophosphate bridging ligands. These nanoclusters fragment into uranium monomers and dimers with mass-to-charge (m/z) ratios in the 280-380 region. The gas phase fragmentation of each cluster studied yields a distinct UO6 - anion attributed to the cleavage of a uranyl ion bound to 2 peroxide groups, along with other anions that can be attributed to the initial composition of the nanoclusters.

Solubility and Thermodynamic Investigation of Meta-Autunite Group Uranyl Arsenate Solids with Monovalent Cations Na and K.

We investigated the aqueous solubility and thermodynamic properties of two meta-autunite group uranyl arsenate solids (UAs). The measured solubility products (log Ksp) obtained in dissolution and precipitation experiments at equilibrium pH 2 and 3 for NaUAs and KUAs ranged from -23.50 to -22.96 and -23.87 to -23.38, respectively. The secondary phases (UO2)(H2AsO4)2(H2O)(s) and trögerite, (UO2)3(AsO4)2·12H2O(s), were identified by powder X-ray diffraction in the reacted solids of KUA precipitation experiments (pH 2) and NaUAs dissolution and precipitation experiments (pH 3), respectively. The identification of these secondary phases in reacted solids suggest that H3O+ co-occurring with Na or K in the interlayer region can influence the solubilities of uranyl arsenate solids. The standard-state enthalpy of formation from the elements (ΔHf-el) of NaUAs is -3025 ± 22 kJ mol-1 and for KUAs is -3000 ± 28 kJ mol-1 derived from measurements by drop solution calorimetry, consistent with values reported in other studies for uranyl phosphate solids. This work provides novel thermodynamic information for reactive transport models to interpret and predict the influence of uranyl arsenate solids on soluble concentrations of U and As in contaminated waters affected by mining legacy and other anthropogenic activities.

Removal of Aqueous Uranyl and Arsenate Mixtures after Reaction with Limestone, PO43-, and Ca2.

The co-occurrence of uranyl and arsenate in contaminated water caused by natural processes and mining is a concern for impacted communities, including in Native American lands in the U.S. Southwest. We investigated the simultaneous removal of aqueous uranyl and arsenate after the reaction with limestone and precipitated hydroxyapatite (HAp, Ca10(PO4)6(OH)2). In benchtop experiments with an initial pH of 3.0 and initial concentrations of 1 mM U and As, uranyl and arsenate coprecipitated in the presence of 1 g L-1 limestone. However, related experiments initiated under circumneutral pH conditions showed that uranyl and arsenate remained soluble. Upon addition of 1 mM PO43- and 3 mM Ca2+ in solution (initial concentration of 0.05 mM U and As) resulted in the rapid removal of over 97% of U via Ca-U-P precipitation. In experiments with 2 mM PO43- and 10 mM Ca2+ at pH rising from 7.0 to 11.0, aqueous concentrations of As decreased (between 30 and 98%) circa pH 9. HAp precipitation in solids was confirmed by powder X-ray diffraction and scanning electron microscopy/energy dispersive X-ray. Electron microprobe analysis indicated U was coprecipitated with Ca and P, while As was mainly immobilized through HAp adsorption. The results indicate that natural materials, such as HAp and limestone, can effectively remove uranyl and arsenate mixtures.

Rigidity and Flexibility: Unraveling the Role of Fulvic Acid in Uranyl Sorption on Graphene Oxide Using Molecular Dynamics Simulations.

Using molecular dynamics simulations, this work targets a molecular understanding on the rigidity and flexibility of fulvic acid (FA) in uranyl sorption on graphene oxide (GO). The simulations demonstrated that both rigid Wang's FA (WFA) and flexible Suwannee River FA (SRFA) can provide multiple sites to cooperate with GO for uranyl sorption and act as "bridges" to connect uranyl and GO to form GO-FA-U (type B) ternary surface complexes. The presence of flexible SRFA was more beneficial to uranyl sorption on GO. The interactions of WFA and SRFA with uranyl were primarily driven by electrostatics, and the electrostatic interaction of SRFA-uranyl was significantly stronger owing to the formation of more complexes. The flexible SRFA could markedly enhance the bonding strength of uranyl with GO by folding itself to provide more sites to coordinate with uranyl. The rigid WFAs tended to be adsorbed on the GO surface in parallel due to π-π interactions, whereas the flexible SRFAs took more slant configurations resulting from intermolecular hydrogen bonds. This work provides new insights into the sorption dynamics, structure, and mechanism and addresses the effect of molecular rigidity and flexibility, with great significance for FA-based remediation strategies of uranium-contaminated sites.

Remediation of uranium-contaminated alkaline soil by rational application of phosphorus fertilizers: Effect and mechanism.

In alkaline soil, abundant carbonates will mobilize uranium (U) and increase its ecotoxicity, which is a serious threat to crop growth. However, the knowledge of U remediation in alkaline soils remains very limited. In this study, U-contaminated alkaline soil (tillage layer) was collected from the Ili mining area of Xinjiang, the soil remediation was carried out by using phosphorus (P) fertilizers of different solubility (including KH2PO4, Ca(H2PO4)2, CaHPO4, and Ca3(PO4)2), and the pathways and mechanisms of U passivation in the alkaline soil were revealed. The results showed that water-soluble P fertilizers, KH2PO4 and Ca(H2PO4)2, were highly effective at immobilizing U, and significantly reduced the bioavailability of soil U. The exchangeable U was reduced by 70.5 ± 0.1% (KH2PO4) and 68.2 ± 1.9% (Ca(H2PO4)2), which was converted into the Fe-Mn oxide-bound and residual phases. Pot experiments showed that soil remediation by KH2PO4 significantly promoted crop growth, especially for roots, and reduced U uptake in crops by 94.5 ± 1.0%. The immobilization of U by KH2PO4 could be attributed to the release of phosphate anions, which react with the uranyl ion (UO22+) forming a stable mineral of meta-ankoleite and enhancing the binding of UO22+ to the soil Fe-Mn oxides. In addition, KH2PO4 dissolution produces acidity and P fertilizer, which can reduce soil alkalinity and improve crop growth. The findings in this work demonstrate that a rational application of P fertilizer can effectively, conveniently, and cheaply remediate U contamination and improve crop yield and safety on alkaline farmland.

Nonthermal plasma-irradiated polyvalent ferromanganese binary hydro(oxide) for the removal of uranyl ions from wastewater.

Nonthermal plasma (NTP) irradiation was employed to adjust the morphological structures and valence distribution of ferromanganese (Fe-Mn)-based binary hydro (oxide) to enhance the heterogeneous adsorption of uranyl ions. The output voltage and the liquid-plate distance played a more vital role among the NTP factors in the irradiation system in influencing the polyvalent Fe-Mn binary hydro (oxide) (poly-Fe-Mn). The formation of plates, flakes, and nanoscale nodules was specifically observed, which caused more pores and fractures in the poly-Fe-Mn binary hydro (oxide). The poly-Fe-Mn performed explicitly better in the adsorption of uranium ions in comparison with the counterpart of the Fe-Mn, which was appropriately fitted by the pseudofirst-order kinetic and Elovich models. Maximum equilibrium adsorption capacities of 663.92 and 923.45 mg/g were obtained for the Fe-Mn and poly-Fe-Mn binary hydro (oxides) toward U ions in the orthogonal design, respectively. The maximum monolayer adsorption capacity achieved by the fitting of the Langmuir model was 1091.10 mg/g. Both physisorption and chemisorption contributed to the heterogeneous process of the poly-Fe-Mn toward uranium ions. The employment of NTP irradiation changed the monolayer adsorption of the traditional Fe-Mn materials and diversified the reaction mechanisms between the interface of the Fe-Mn materials and uranium ions. The elements, including O, N, and U exhibited higher compatibility and overlapped in the samples. The highly effective capture of uranium ions from the solution by the poly-Fe-Mn binary hydro (oxide) was mainly related to the chemical deposition of O and N radicals.

Kinetics of Na- and K- uranyl arsenate dissolution.

We integrated aqueous chemistry analyses with geochemical modeling to determine the kinetics of the dissolution of Na and K uranyl arsenate solids (UAs(s)) at acidic pH. Improving our understanding of how UAs(s) dissolve is essential to predict transport of U and As, such as in acid mine drainage. At pH 2, Na0.48H0.52(UO2)(AsO4)(H2O)2.5(s) (NaUAs(s)) and K0.9H0.1(UO2)(AsO4)(H2O)2.5(s) (KUAs(s)) both dissolve with a rate constant of 3.2 × 10-7 mol m-2 s-1, which is faster than analogous uranyl phosphate solids. At pH 3, NaUAs(s) (6.3 × 10-8 mol m-2 s-1) and KUAs(s) (2.0 × 10-8 mol m-2 s-1) have smaller rate constants. Steady-state aqueous concentrations of U and As are similarly reached within the first several hours of reaction progress. This study provides dissolution rate constants for UAs(s), which may be integrated into reactive transport models for risk assessment and remediation of U and As contaminated waters.

Investigation of the Efficacy of Lanthanoid Heavy Metal Acetates as Electron Staining Reagents for Biomembrane Vesicles.

Transmission electron microscopy (TEM) has revolutionized our understanding of protein structures by enabling atomic-resolution visualization without the need for crystallography, thanks to advancements in cryo-TEM and single particle analysis methods. However, conventional electron microscopy remains relevant for studying stained samples, as it allows the practical determination of optimal conditions through extensive experimentation. TEM also facilitates the examination of supramolecular complexes encompassing proteins, lipids, and nucleic acids. In this study, we investigated the applicability of lanthanoid reagents as electron-staining alternatives to uranyl acetate, which is globally regulated as a nuclear fuel material. We focus on a model biomembrane vesicle system, the chromatophores from the purple photosynthetic eubacterium Rhodospirillum rubrum, which integrate proteins and lipids. Through density distribution analysis of electron micrographs, we evaluated the efficacy of various lanthanoid acetates and found that triacetates of neodymium, samarium, and gadolinium exhibited similar staining effectiveness to uranyl acetate. Additionally, triacetates of praseodymium, erbium, and lutetium, followed by europium show promising results as secondary candidates. Our findings suggest that lanthanoid transition heavy metal acetates could serve as viable alternatives for electron staining in TEM, offering potential advantages over uranyl acetate.

Organically Templated Uranyl Sulfates and Selenates: Structural Complexity and Crystal Chemical Restrictions for Isotypic Compounds Formation.

This paper reviews the state of the art in the structural chemistry of organically templated uranyl sulfates and selenates, which are considered as the most representative groups of U-bearing synthetic compounds. In total, there are 194 compounds known for both groups, the crystal structures of which include 84 various organic molecules. Structural studies and topological analysis clearly indicate complex crystal chemical limitations in terms of the isomorphic substitution implementation, since the existence of isotypic phases has to date been confirmed only for 24 compounds out of 194, which is slightly above 12%. The structural architecture of the entire compound depends on the combination of the organic and oxyanion parts, changes in which are sometimes realized even while maintaining the topology of the U-bearing complex. An increase in the size of the hydrocarbon part and number of charge functional groups of the organic cation leads to the formation of rare and more complex topologies. In addition, the crystal structures of two novel uranyl sulfates and one uranyl selenate, templated by isopropylammonium cations, are reported.

Covalency between the uranyl ion and dithiophosphinate by sulfur K-edge X-ray absorption spectroscopy and density functional theory.

The dithiophosphinic acids (HS2PR2) have been used for the selective separation of trivalent actinides (AnIII) from lanthanides (LnIII) over the past decades. The substituents on the dithiophosphinic acids dramatically impact the separation performance, but the mechanism is still open for debate. In this work, two dithiophosphinic acids with significantly different AnIII/LnIII separation performance, i.e. diphenyl dithiophosphinic acid (HS2PPh2) and bis(ortho-trifluoromethylphenyl) dithiophosphinic acid [HS2P(o-CF3C6H4)2], are employed to understand the substituent effect on the bonding covalency between the S2PR2- anions (R = Ph and o-CF3C6H4) and the uranyl ion by sulfur K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory calculations. The two UO2(S2PR2)(EtOH) complexes display similar XAS spectra, in which the first pre-edge feature with an intensity of 0.16 is entirely attributed to the transitions from S 1s orbitals to the unoccupied molecular orbitals due to the mixing between U 5f and S 3p orbitals. The Mulliken population analysis indicates that the amount of \% S 3p character in these orbitals is essentially identical for the UO2(S2PPh2)2(EtOH) and UO2[S2P(o-CF3C6H4)2]2(EtOH) complexes, which is lower than that in the U 6d-based orbitals. The essentially identical covalency in U-S bonds for the two UO2(S2PR2)2(EtOH) complexes are contradictory to the significantly different AnIII/LnIII separation performance of the two dithiophosphinic acids, thus the covalency seems to be unable to account for substituent effects in the AnIII/LnIII separation by the dithiophosphinic acids. The results in this work provide valuable insight into the understanding of the mechanism in the AnIII/LnIII separation by the dithiophosphinic acids.

Potassium permanganate is an excellent alternative to osmium tetroxide in freeze-substitution.

High-pressure freezing followed by freeze-substitution is a valuable method for ultrastructural analyses of resin-embedded biological samples. The visualization of lipid membranes is one of the most critical aspects of any ultrastructural study and can be especially challenging in high-pressure frozen specimens. Historically, osmium tetroxide has been the preferred fixative and staining agent for lipid-containing structures in freeze-substitution solutions. However, osmium tetroxide is not only a rare and expensive material, but also volatile and toxic. Here, we introduce the use of a combination of potassium permanganate, uranyl acetate, and water in acetone as complementing reagents during the freeze-substitution process. This mix imparts an intense en bloc stain to cellular ultrastructure and membranes, which makes poststaining superfluous and is well suited for block-face imaging. Thus, potassium permanganate can effectively replace osmium tetroxide in the freeze-substitution solution without sacrificing the quality of ultrastructural preservation.

Tetra-Substituted p-Tert-Butylcalix[4]Arene with Phosphoryl and Salicylamide Functional Groups: Synthesis, Complexation and Selective Extraction of f-Element Cations.

A new series of lanthanide (1-5) and uranyl (6) complexes with a tetra-substituted bifunctional calixarene ligand H2 L is described. The coordination environment for the Ln3+ and UO2 2+ ions is provided by phosphoryl and salicylamide functional groups appended to the lower rim of the p-tert-butylcalix[4]arene scaffold. Ligand interactions with lanthanide cations (light: La3+ , Pr3+ ; intermediate: Eu3+ and Gd3+ ; and heavy: Yb3+ ), as well as the uranyl cation (UO2 2+ ) is examined in the solution and solid state, respectively with spectrophotometric titration and single crystal X-ray diffractometry. The ligand is fully deprotonated in the complexation of trivalent lanthanide ions forming di-cationic complexes 2 : 2 M : L, [Ln2 (L)2 (H2 O)]2+ (1-5), in solution, whereas uranyl formed a 1 : 1 M : L complex [UO2 (L)(MeOH)]∞ (6) that demonstrated very limited solubility in 12 organic solvents. Solvent extraction behaviour is examined for cation selectivity and extraction efficiency. H2 L was found to be an effective extracting agent for UO2 2+ over La3+ and Yb3+ cations. The separation factors at pH 6.0 are: ßUO 2 2 + /La 3 + =121.0 and ßUO 2 2 + /Yb 3 + =70.0.