Effect of humic acid on the solid phase stability and solubility of UO<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>

The stability and solubility of UO₂(OH)₂ has been studied as a function of the humic acid concentration in 0.1M NaClO₄, in the pH range from 4 to 7 under normal atmospheric conditions. The solid phase under investigation has been prepared by alkaline precipitation and characterized by TGA, ATR-FTIR, XRD, SEM and solubility measurements. According to the experimental data UO₂(OH)₂ is stable and remains the solubility limiting solid phase even in the presence of increased humic acid concentration in the solution. However, humic acid affects texture and particle size of the solid phase. Increasing humic acid concentration results in decreasing crystallite size of the UO₂(OH)₂ solid phase. Based on the solubility data, the logK _sp (UO₂(OH)₂) has been evaluated to be −22.0±0.3 and the stability constant for the UO₂(OH)HA(I) species has been estimated to be logβ ₁₁₀₁ = 15.3±0.5.     

Chemistry of the CARBEX process: Identification of absorption bands of the ligands in the electronic spectra of aqueous solutions of Na<Subscript>4</Subscript>[UO<Subscript>2</Subscript>(CO<Subscript>3</Subscript>)<Subscript>3</Subscript>]

On the basis of consideration of hydration, hydrolysis, dissociation, polymerization, and ligand exchange that occur in aqueous solutions of U(VI) complexes, a new approach to the assignment of absorption bands of the ligands in electronic spectra of uranium(VI) carbonate complexes in the range 190–400 nm has been suggested. For the Na₄[UO₂(CO₃)₃] complex, the following assignment of absorption bands has been made: Na₃[UO₂(CO₃)₃]^–, 258 nm; Na₂[UO₂(CO₃)₃]^2–, 300 nm; and Na₄[UO₂(CO₃)₃], 330 nm.     

Constant current anodic stripping chronopotentiometric determination of uranium in uranium mineral ores via accumulation of K<Subscript>2</Subscript>UO<Subscript>2</Subscript>[Fe(CN)<Subscript>6</Subscript>] on the palladium plated aluminum electrode

In the present work the uranyl hexacyanoferrate (K₂UO₂[Fe(CN)₆]) is deposited on the palladized aluminum (Pd-Al) electrode from a \textUO₂^{2 +} + \textFe( \textCN )₆ ^{- 3} {\text{UO}}_{2}^{2 + } + {\text{Fe}}\left( {\text{CN}} \right)_{6}^{ - 3} solution. Then the anodic stripping chronopotentiometry (ASCP) was used to strip the K₂UO₂[Fe(CN)₆] from the Pd-Al surface. The operational conditions including: pH, K₃Fe(CN)₆ concentration, deposition potential, deposition time and stripping current were optimized. The ASCP calibration graph was linear in concentration range 10–460 μM. of \textUO₂^{2 +} {\text{UO}}_{2}^{2 + } and the detection limit was 8.5 μM. The interference of some concomitant ions during the deposition process of K₂UO₂[Fe(CN)₆] was studied. The proposed method was successfully applied for analysis of some uranium mineral ores.     

Template‐Free Synthesis and Mechanistic Study of Porous Three‐Dimensional Hierarchical Uranium‐Containing and Uranium Oxide Microspheres

A novel type of uranium‐containing microspheres with an urchin‐like hierarchical nano/microstructure has been successfully synthesized by a facile template‐free hydrothermal method with uranyl nitrate hexahydrate, urea, and glycerol as the uranium source, precipitating agent, and shape‐controlling agent, respectively. The as‐synthesized microspheres were usually a few micrometers in size and porous inside, and their shells were composed of nanoscale rod‐shaped crystals. The growth mechanism of the hydrothermal reaction was studied, revealing that temperature, ratios of reactants, solution pH, and reaction time were all critical for the growth. The mechanism study also revealed that an intermediate compound of 3 UO₃?NH₃?5 H₂O was first formed and then gradually converted into the final hydrothermal product. These uranium‐containing microspheres were excellent precursors to synthesize porous uranium oxide microspheres. With a suitable calcination temperature, very uniform microspheres of uranium oxides (UO_2+x, U₃O₈, and UO₃) were successfully synthesized.     

High Impact of Uranyl Ions on Carrying–Releasing Oxygen Capability of Hemoglobin‐Based Blood Substitutes

The effect of radioactive UO₂²⁺ on the oxygen‐transporting capability of hemoglobin‐based oxygen carriers has been investigated in vitro. The hemoglobin (Hb) microspheres fabricated by the porous template covalent layer‐by‐layer (LbL) assembly were utilized as artificial oxygen carriers and blood substitutes. Magnetic nanoparticles of iron oxide (Fe₃O₄) were loaded in porous CaCO₃ particles for magnetically assisted chemical separation (MACS). Through the adsorption spectrum of magnetic Hb microspheres after adsorbing UO₂²⁺, it was found that UO₂²⁺ was highly loaded in the magnetic Hb microspheres, and it shows that the presence of UO₂²⁺ in vivo destroys the structure and oxygen‐transporting capability of Hb microspheres. In view of the high adsorption capacity of UO₂²⁺, the as‐assembled magnetic Hb microspheres can be considered as a novel, highly effective adsorbent for removing metal toxins from radiation‐contaminated bodies, or from nuclear‐power reactor effluent before discharge into the environment.     

Chemistry of the CARBEX process: Identification of absorption bands of the ligands in the electronic spectra of aqueous solutions of Na<Subscript>4</Subscript>[UO<Subscript>2</Subscript>(O<Subscript>2</Subscript>)CO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

On the basis of consideration of dissociation, hydration, association, and ligand exchange, the assignment of absorption bands in the electronic spectra of aqueous solutions of the Na₄[UO₂(O₂)CO₃)₂] complex has been performed. It has been demonstrated that the absorption in the range 190–400 nm is caused by the oxygen atoms of the O₂^2- and CO₃^2- groups and hydration water molecules of dissociated and neutral complex species Na₃[UO₂(O₂)(CO₃)₂]^–, Na₂[UO₂(O₂)(CO₃)₂]^2–, and Na₄[UO₂(O₂)(CO₃)₂].     

Extraction of pertechnetates from HNO<Subscript>3</Subscript> solutions into ionic liquids

The effect of the oxidation temperature of sintered UO₂ pellets on the powder properties of U₃O₈ was studied in the temperature range 250–900 °C in air. The U₃O₈ was obtained at 450 °C after 180 min and its particle size and surface area are respectively, 35 µm and 0.7 m²/g. The reduction of the U₃O₈ powder resulted in UO₂ after 30 min with a surface area of 0.8 m²/g. This value was improved more than 3.5 times by applying five alternating oxidation–reduction cycles.     

Controlled synthesis and enhanced bacteriostatic activity of Mg(OH)<Subscript>2</Subscript>/Ag nanocomposite

Silver nanoparticles have good sterilization performance due to their small size and large specific surface area, while the small size also brings about reunification and reduces the sterilization activity. To resolve the problem, magnesium hydroxide [Mg(OH)₂] microsphere was designed as a supported material to load silver particles on its surface. Mg(OH)₂ microspheres were successfully synthesized under the control of a biotemplate of eggshell membrane. X-ray diffraction, thermal gravimetric analysis/differential scanning calorimetry, and transmission electron microscopy were performed to characterize the Mg(OH)₂ microspheres. The results indicate that the Mg(OH)₂ microspheres of average size ~ 2 μm were formed from nanoflakes. The silver nanoparticles were loaded on the surface of Mg(OH)₂ microspheres to form Mg(OH)₂/Ag nanocomposite, which exhibited enhanced antibacterial effect compared to that of silver nanoparticles. The enhanced antibacterial mechanism was investigated in detail.     

Crystal and molecular structure of ammonium trinitratouranylate NH<Subscript>4</Subscript>[UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>]

Ammonium trinitratouranylate NH₄[UO₂(NO₃)₃] (I) single crystals have been synthesized by the reaction of aqueous solutions of diaquadinitratouranyl tetrahydrate and ammonium nitrate in the presence of nitric acid. The structure of the complex has been studied by X-ray diffraction analysis: space group \(R\bar 3c\), a = 9.361(2), c = 18.883(4) Å; V = 1433.0(5) ų, and Z = 6. The structural units of the NH₄[UO₂(NO₃)₃] crystal—NH ₄ ⁺ cations and [UO₂(NO₃)₃]^? complex anions with three bidentate cyclic nitrato groups—are on crystallographic axes \(\bar 3\). A complex three-dimensional packing arranged by the electrostatic attraction forces between counterions and the N-H...O hydrogen bonds between ammonium cations and trinitratouranylate anions is realized in the structure. X-ray diffraction analysis results are confirmed by IR spectra of NH₄[UO₂(NO₃)₃].     

Synthesis and crystal structure of (NH<Subscript>4</Subscript>)(CN<Subscript>3</Subscript>H<Subscript>6</Subscript>)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of (NH₄)(CN₃H₆)[UO₂(SeO₃)₂] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) Å, b = 9.4234(3) Å, c = 9.5408(3) Å, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P ₁, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO₂(SeO₃)₂]^2? chains of the crystal-chemical group AB²B₁₁ (A = UO ₂ ²⁺ , B₂= SeO₃ ^2?, B₁₁= SeO₃ ^2?) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Structure and some properties of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>{CH<Subscript>3</Subscript>CON(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

A new complex [UO₂CrO₄{CH₃CON(CH₃)₂}₂] (I) was studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are monoclinic: a = 13.8108(11) Å, b = 8.6804(7) Å, c = 13.0989(10) Å, β = 104.777(1)°, V = 1518.4(2) ų, space group P2₁/c, Z = 4, R = 2.39%. The structure of I contains infinite chains of the [UO₂CrO₄{CH₃CON(CH₃)₂}₂] composition running along [001]; the complex belongs to the AT¹¹M¹ ₂ crystal-chemical group (A = UO ₂ ²⁺ , T¹¹ = CrO ₄ ^2? , M¹ = CH₃CON(CH₃)₂) of uranyl complexes. The chains are linked into a three-dimensional framework due to hydrogen bonds between oxygen atoms of chromate ions and hydrogen atoms of methyl groups of the dimethylacetamide.     

Fluorinated Mesoporous Anatase TiO<Subscript>2</Subscript> Microspheres with High Surface and Enhanced Photocatalytic Activity for the Degradation of Methyl Orange

Highly crystalline mesoporous TiO₂ microspheres with areas up to 122 m²/g and tunable pore size have been prepared through a combined sol–gel and solvothermal processes. The concentration of NaF exhibits a great effect on the morphology, crystallinity, crystal size and photocatalytic activity of the TiO₂ microspheres. A higher NaF concentration results in an increase in the average crystal size and pore size, whereas whereas it caused a decrease in the specific surface areas. All fluorinated TiO₂ microspheres showed a higher photocatalytic activity than P25 and pure TiO₂ microspheres obtained in the absence of NaF due to the effect of surface fluorination on the photoactivity of TiO₂. The approach described in this study provides a simple method to synthesize the micrometer-sized hierarchical structure of mesoporous TiO₂ microspheres that are ready for practical applications such as environmental pollutants removal and solar cell because these high active materials can be easily separated.     

Direct dissolution of intact UO<Subscript>2</Subscript> pellet and in situ extraction by organic solutions of TBP-HNO<Subscript>3</Subscript> at atmospheric pressure: role of solvate composition

Recently authors demonstrated direct dissolution of g-level PHWR UO₂ fuel pellet fragments and in situ extraction by TBP-HNO₃ and TiAP-HNO₃ solutions at atmospheric pressures. Extending the work, similar studies were performed on intact unirradiated PHWR UO₂ fuel pellets (~15 g U) with varying compositions of organic solvate of tri-n-butyl phosphate (TBP). It was observed that extent of dissolution was a strong function of organic solution composition TBP·(HNO₃) _x (H₂O) _y . Complete dissolution of intact UO₂ pellet in a reasonable time was observed only in case of a particular solvate composition.     

Crystal Structure of [UO<Subscript>2</Subscript>SO<Subscript>4</Subscript>{(CH<Subscript>3</Subscript>)HNCONH(CH<Subscript>3</Subscript>)}<Subscript>2</Subscript>]

The single crystals of [UO₂SO₄{(CH₃)HNCONH(CH₃)}₂] (I) were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 6.847(1) Å, b = 14.259(3) Å, c = 14.297(3) Å, β = 93.451(4)°, space group P2₁/n, Z = 4. The main structural units of crystals I are ribbons whose composition coincides with the composition of the compound. The crystal chemical formula of the complex is AT³M ₂ ¹ (A = UO ₂ ²⁺ ).     

Resonant emission of UO<Subscript>2</Subscript>, U<Subscript>3</Subscript>O<Subscript>8</Subscript>, and UO<Subscript>2+<Emphasis Type="Italic">x</Emphasis></Subscript> valence electrons under SR excitation near the O<Subscript>4,5</Subscript>(U) absorption edge

The structure of the resonant electron emission (REE) spectra of UO₂ (REE appears under the excitation with synchrotron radiation near the O_4,5(U) absorption edge at ∼100 eV and ∼110 eV) is studied with regard to the X-ray O_4,5(U) absorption spectrum of UO₂ and a quantitative scheme of molecular orbitals based on the X-ray electron spectroscopy data and the results of a relativistic calculation of the electronic structure of UO₂. The structure of the REE spectra of U₃O₈ and UO_2+x is studied for comparison, and the effect of the uranium chemical environment in oxides on it is found. The appearance of such a structure reflects the processes of excitation and decay involving the U5d and electrons of the outer valence MOs (OVMOs, from 0 to ∼13 eV) and inner valence MOs (IVMOs, from ∼13 eV to ∼35 eV) of the studied oxides. It is noted that REE spectra show the partial density of states of U6p and U5f electrons. Based on the structure of REE spectra, it is revealed that U5f electrons directly participate (without losing the f nature) in the chemical bonding of uranium oxides and are delocalized within CMOs (in the middle of the band), which results in the enhancement of the intensity of the REE spectra of CMO electrons during resonances. The U6d electrons are found to be localized near the bottom of the outer valence band and are observed in the REE spectra of the studied oxides as a characteristic maximum at 10.8 eV. It is confirmed that U6p electrons are effectively involved in the formation of IVMOs, which leads to the appearance of the structure in the region of IVMO electron energies during resonances. This structure depends on the chemical environment of uranium in the considered oxides.     

Impact of environmental conditions on the sorption behavior of UO<Subscript>2</Subscript><Superscript>2+</Superscript> onto attapulgite studied by batch experiments

The sorption of UO₂ ²⁺ from aqueous solution on attapulgite was investigated as a function of contact time, solid content, pH, ionic strength, foreign ions, humic acid (HA), and fulvic acid (FA) under ambient conditions by using batch technique. The attapulgite sample was characterized by XRD and FTIR in detail. The results indicated that the sorption of UO₂ ²⁺ was strongly dependent on pH and ionic strength. The sorption of UO₂ ²⁺ on attapulgite increased quickly with rising pH at pH < 6.5, and decreased with increasing pH at pH > 6.5. The presence of HA or FA enhanced the sorption of UO₂ ²⁺ on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA/FA with UO₂ ²⁺ on attapulgite surface. Sorption of UO₂ ²⁺ on attapulgite was mainly dominated by ion-exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation at high pH values. The results indicate that attapulgite is a very suitable adsorbent for the preconcentration and solidification of UO₂ ²⁺ from large volumes of aqueous solutions because of its negative surface charge and large surface areas.     

Uranyl cyanoacetate [UO<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(NCCH<Subscript>2</Subscript>COO)<Subscript>2</Subscript>]: Synthesis,crystal structure,and absorption spectra

The U(VI) complex with cyanoacetic acid, [UO₂(H₂O)₂(NCCH₂COO)₂] (I), was synthesized from an aqueous solution, and its X-ray diffraction analysis was carried out. The crystals are orthorhombic: space group Pca2 ₁, a = 25.9605(7) Å, b = 6.7634(2) Å, c = 6.3398(2) Å, V = 1113.15(6) ų at 100 K, and Z = 4. The coordination polyhedron of the uranium atom is a distorted pentagonal bipyramid. The cations UO ₂ ²⁺ are bound into infinite zigzag chains by the bridging carboxyl groups of one of the anions of cyanoacetic acid. The carboxyl oxygen atom of the second anion, which is not involved in coordination, and the nitrogen atoms of the cyano groups form hydrogen bonds with the coordination water molecules. The layer structure of the compound is formed through the hydrogen bonds. The absorption spectra in the visible and infrared ranges of the crystalline compound are measured and analyzed.     

Structure and some properties of [UO<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)(C<Subscript>5</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]

The complex [UO₂(SeO₄)(C₅H₁₂N₂O)₂(H₂O)] (I) was synthesized and studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are orthorhombic: a = 13.1661(3) Å, b = 16.4420(5) Å, c = 17.4548(6) Å, Pbca, Z = 8, R = 0.0423. The structural units of crystal I are chains with the composition coinciding with that of the compounds of the AB₂M ₃ ¹ crystal chemical group of the uranyl complexes (A = UO ₂ ²⁺ , B² = SeO ₄ ^2? , M¹ = C₅H₁₂N₂O and H₂O).     

Synthesis and study of sodium triuranate Na<Subscript>2</Subscript>(UO<Subscript>2</Subscript>)<Subscript>3</Subscript>O<Subscript>3</Subscript>(OH)<Subscript>2</Subscript>

Sodium triuranate Na₂(UO₂)₃O₃(OH)₂ was synthesized by the reaction between aqueous uranyl acetate solution and aqueous sodium nitrate solution under hydrothermal conditions at 200°C. The composition and structure of the synthesized compound were determined, and its dehydration and thermal decomposition were studied, by chemical analysis, X-ray diffraction, IR spectroscopy, and thermal analysis.