Three Mechanisms in One Material: Uranium Capture by a Polyoxometalate–Organic Framework through Combined Complexation,Chemical Reduction,and Photocatalytic Reduction

The design and synthesis of uranium sorbent materials with high uptake efficiency, capacity and selectivity, as well as excellent hydrolytic stability and radiation resistance remains a challenge. Herein, a polyoxometalate (POM)–organic framework material ( SCU‐19 ) with a rare inclined polycatenation structure was designed, synthesized through a solvothermal method, and tested for uranium separation. Under dark conditions, SCU‐19 can efficiently capture uranium through ligand complexation using its exposed oxo atoms and partial chemical reduction from U^VI to U^IV by the low‐valent Mo atoms in the POM. An additional U^VI photocatalytic reduction mechanism can occur under visible light irradiation, leading to a higher uranium removal without saturation and faster sorption kinetics. SCU‐19 is the only uranium sorbent material with three distinct sorption mechanisms, as further demonstrated by X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption near edge structure (XANES) analysis.     

Three Mechanisms in One Material: Uranium Capture by a Polyoxometalate–Organic Framework through Combined Complexation,Chemical Reduction,and Photocatalytic Reduction

The design and synthesis of uranium sorbent materials with high uptake efficiency, capacity and selectivity, as well as excellent hydrolytic stability and radiation resistance remains a challenge. Herein, a polyoxometalate (POM)–organic framework material ( SCU‐19 ) with a rare inclined polycatenation structure was designed, synthesized through a solvothermal method, and tested for uranium separation. Under dark conditions, SCU‐19 can efficiently capture uranium through ligand complexation using its exposed oxo atoms and partial chemical reduction from U^VI to U^IV by the low‐valent Mo atoms in the POM. An additional U^VI photocatalytic reduction mechanism can occur under visible light irradiation, leading to a higher uranium removal without saturation and faster sorption kinetics. SCU‐19 is the only uranium sorbent material with three distinct sorption mechanisms, as further demonstrated by X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption near edge structure (XANES) analysis.     

Civilian and military uses of depleted uranium: environmental and health problems

Depleted uranium is a by-product of the process of enrichment of natural uranium and is classified as a toxic and radioactive waste; it has a very high density (approximately 19 g cm-3), a remarkable ductility and a cost low enough to be attractive for some particular technical applications. Civilian uses are essentially related to its high density, but the prevailing use is however military (production of projectiles). From the radioactive point of view, the exposure to depleted uranium can result from both external irradiation as well as internal contamination. The associated risks are however mainly of chemical-toxicological kind and the target organ is the kidney. In the present note the recent military uses and the possible effects of its environmental diffusion are discussed.     

Photochemical reduction of uranyl ion with ditertiary phosphines in dry acetone

Time-resolved transient absorption spectra have been observed using monochromatic light (=347.1 nm) from a 25 ns pulsed ruby laser. Collision between optically excited uranyl ion and ditertiary phosphines lead to photochemical reduction of uranyl ion to uranium(V) in non-aqueous medium. Stern-Volmer constants measured from lifetime measurement and quantum yields for uranium(V) formation reveal that electron transfer phenomenon competes with photophysical deactivation because of the presence of phenyl groups. Since ditertiary phosphines have two electron donating phosphorus atoms, are better reductant than monodentate phosphines in non aqueous medium.     

X-ray absorption fine structure spectroscopic study of uranium nitrides

Uranium mononitride (UN), sesquinitride (U₂N₃) and dinitride (UN₂) were characterized by extended X-Ray absorption fine structure spectroscopy. Analysis on UN indicate the presence of three uranium shells at distances of 3.46(3), 4.89(5) and 6.01(6) Å and a nitrogen shell at a distance of 2.46(2) Å. For U₂N₃, two absorbing uranium atoms at different crystallographic positions are present in the structure. One of the uranium atoms is surrounded by nitrogen atoms at 2.28(2) Å and by uranium atoms at 3.66(4) and 3.95(4) Å. The second type of uranium atom is surrounded by nitrogen atoms at 2.33(2) and 2.64(3) Å and by uranium atoms at 3.66(4), 3.95(4) and 5.31(5) Å. Results on UN₂ indicate two uranium shells at 3.71(4) and 5.32(5) Å and two nitrogen shells at 2.28(2) and 4.34(4) Å. The lattice parameters of UN, U₂N₃ and UN₂ unit cells were respectively determined to be 4.89(5), 10.62(10) and 5.32(5) Å. Those results are well in agreement with those obtained by X-Ray diffraction analysis.     

Infrared spectrum and bonding in uranium methylidene dihydride, CH2=UH2

Uranium atoms activate methane upon ultraviolet excitation to form the methyl uranium hydride CH3-UH, which undergoes alpha-H transfer to produce uranium methylidene dihydride, CH2=UH2. This rearrangement most likely occurs on an excited-quintet potential-energy surface and is followed by relaxation in the argon matrix. These simple U+CH4 reaction products are identified through isotopic substitution (13CH4, CD4, CH2D2) and density functional theory frequency and structure calculations for the strong U-H stretching modes. Relativistic multiconfiguration (CASSCF/CASPT2) calculations substantiate the agostic distorted C1 ground-state structure for the triplet CH2=UH2 molecule. We find that uranium atoms are less reactive in methane activation than thorium atoms. Our calculations show that the CH2=UH2 complex is distorted more than CH2=ThH2. A favorable interaction between the low energy open-shell U(5f) sigma orbital and the agostic hydrogen contributes to the distortion in the uranium methylidene complexes.     

Uranium and thorium abundances in chondritic meteorites

Neutron-activation analyses for uranium and thorium are reported for 42 chondrite meteorite "falls" and 1 "find" covering 15 of the 20 Van Schmus-Wood chondrite types. The mean uranium and thorium abundances of the 5 chemical groups show a trend with C group (U = 0.012(0) atoms/10(6) Si atoms, Th = 0.045(4) atoms/10(6) Si atoms, Th U = 3.7(8)) > H, L and LL groups (U = 0.008(3), Th = 0.028(0), Th U = 3.4(5)) > E group (U = 0.005(9), Th = 0.021(8), Th U = 3.6(9)). With the possible exception of the C3 chondrites, the mean abundances for each petrologic type within a given chemical group are identical.     

Die Kristallstruktur einer triklinen Modifikation von Uranpentachlorid

The Crystal Structure of a Triclinic Modification of Uranium Pentachloride From solution uranium pentachloride crystallizes at room temperature in a triclinic modification belonging to the space group P1 . The unit cell contains one formula unit (UCl₅)₂ and has the dimensions a = 707, b = 965, c = 635 pm and α = 0.495 π, β = 0.652 π, γ = 0.603 π rad. The crystal structure was solved with the aid of X-ray diffraction data and was refined to a reliability index of R = 0.082. The structure consists of (UCl₅)₂ molecules having the point symmetry mmm in which the uranium atoms are linked with one another via two chlorine atoms. The crystal lattice can be derived from a hexagonal closest packing of chlorine atoms in which 1/5 of all octahedral holes are occupied by uranium atoms.     

Ore Leashing Processing for Yellow Cake Production and Assay of their Uranium Content by Radiometric Analysis

In this study, Ore granite samples were collected from Gattar site for leashing of yellow cake. The process involves heap leaching of uranium through four main steps; size reduction, leaching, uranium purification, and finally precipitation and filtration. The separation process has been given in details and as flow chart. Gamma spectrometry based on HpGe detector and energy dispersive X‐ray (EDX) were used to assay uranium content and activity before and after separation. The uranium weight percentage value as measured by EDX were found to be 40.5 and 67.5 % before and after purification respectively. The results of the calculations based on gamma measurements show high uranium activity and the uranium activity ratios values are 0.045 ± 4.9, 0.043 ± 4.7, and 0.046 ± 2.3 %, before purification, whereas these values were found to be 0.050 ± 3.3, 0.049 ± 3.3, and 0.050 ± 2.7 %, after purification, respectively. The results are discussed in details in the paper.     

Coulometric titration of uranium and uranium-vanadium mixtures with +3 titanium

Coulometric titration of + 6 uranium with electrogenerated titanous ion at a platinum cathode in 8F sulfuric acid can be performed accurately in the presence of ferrous ion as a catalyst Ampero-metric end-point detection is employed. The titration is suitable for the precise assay of uranium compounds. Mixtures of +5 vanadium and +6 uranium can be titrated, because the reduction of +5 vanadium occurs at a more oxidizing potential than the reduction of +4 vanadium and +6 uranium. Using amperometric end-point detection, two end-points are observed corresponding to the reduction of +5 vanadium to the +4 state, and to the simultaneous reduction of + 4 vanadium to the +3 state and +6 uranium to the +4 state. Errors are as small as + 0.3%, provided the uraninium/vanadium ratio is between 0.1 and 10.     

Theoretical study of the reduction of uranium(VI) aquo complexes on titania particles and by alcohols

To provide insights into the adsorption and photoreduction of uranium(VI) on TiO(2), we have studied the structural and electronic properties of uranium(VI) aquo complexes adsorbed on stoichiometric and defected TiO(2) surfaces and nanoparticles. Plane wave calculations with the pure PBE density functional and the PBE+U approach were used to study U(VI) complexes on a periodic rutile (110) slab. In addition, a nanoparticulate Ti(38)O(76) cluster was used to simulate anatase nanoparticles. The electronic structures of the adsorbed U(VI) complexes indicate that the photoreduction process is a consequence of the photocatalytic properties of TiO(2). The reduction of the adsorbed complexes can only occur if the energy of the incident photon exceeds the semiconductor band gap. The gap states induced by single or neighboring hydrogen atoms and oxygen vacancies at the rutile (110) surface cannot reduce adsorbed U(VI) complexes as the unoccupied 5f orbitals are found deeper in the conduction band. In the absence of a solid substrate, photoreduction proceeds by abstraction of a hydrogen atom from water or organic molecules present in solution. Photoreduction by chlorophenol results in lower product yield than reduction by aliphatic alcohols. This is because the triplet uranyl-chlorophenol complex is much more stable than similar complexes formed with methanol and ethanol. In the case of water, the hydroxyl photoproduct easily re-oxidizes the pentavalent species formed. In addition, it is easier for the triplet uranyl-water complex to decompose to the photoreactants.     

Recycling of uranium containing alkaline waste solution generated in the preparation of UO3 microspheres by the internal gelation process

Summary A recent study has indicated the feasibility of recycling of chemicals from alkaline waste generated in the preparation of UO₃ microspheres by the internal gelation process. Present paper investigates the recycle process, the volume of the secondary uranium waste. Result shows that prior to start the recycle process, the waste solution should be freed from uranium by ion-exchange. Optimized experimental condition to achieve maximum reduction in the volume of uranium based waste is discussed.     

Studies on the partitioning of actinides from high level liquid waste solution employing supported liquid membrane with Cyanex-923 as carrier

The present paper deals with the studies on the partitioning of actinides from high level liquid waste solution of PUREX origin employing supported liquid membrane technique. The process uses solution of Cyanex-923 in n-dodecane as a carrier with poly tetra fluoro ethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Transport studies are carried out for ²⁴¹Am under different experimental conditions to optimize the transport parameters such as feed acidity, carrier concentration, effect of uranium, trivalent metal ion and salt concentration in the feed. Studies indicated good transport of actinides across the membrane from nitric acid medium. Under the optimized conditions the transport of ²⁴¹Am is studied from a uranium depleted synthetic PHWR-HLLW and finally the technique has been used for the partitioning of alpha emitters from an actual research reactor-HLLW. High concentration of uranium in the feed is found to retard the transport of americium, suggesting the need for prior removal of uranium from the waste.     

Formation and characterization of the uranium methylidene complexes CH2 = UHX (X = F, Cl, and Br)

The reactions between uranium atoms and CH3X (X = F, Cl, and Br) molecules are investigated in a solid argon matrix. The major products formed on ultraviolet irradiation are the CH2=UHX methylidene complexes. DFT calculations predict these triplet ground-state structures to be stable and to have significant agostic interactions. Parallels between the uranium and analogous thorium methylidene complexes are discussed.     

Actinide tetra-N-heterocyclic carbene ‘sandwiches’

Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms. The complexes were characterized by a range of experimental methods and DFT calculations. X-ray crystallography confirms the geometry at the metal centre can be set by the size of the macrocyclic ring, leading to either square prismatic or square anti-prismatic shapes; the geometry of the latter is retained in solution, which also undergoes reversible, electrochemical one-electron oxidation or reduction for the uranium variant. DFT calculations reveal a frontier orbital picture that is similar to thorocene and uranocene, in which the NHC ligands show almost exclusively σ-donation to the metal without π-backbonding.

Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms.     

Reduction of oxide ions of uranium in single-filament surface-ionization mass spectrometry with application to rock samples

Ion-emission characteristics of a single-filament surface-ionization source for uranium are described. It is shown that a graphite coating over uranium samples enhances reduction of oxides to U⁺ and improves quantitative performance. Results obtained for uranium in several rock samples are in reasonable agreement with results reported by others.     

Density functional study of O2 adsorption on (100) surface of γ‐uranium

Chemisorption of the oxygen molecule on the (100) surface of γ‐uranium was investigated using the generalized gradient approximation to Density Functional Theory. Dissociative adsorptions of O₂ are found to be significantly favored compared to molecular adsorptions. Interstitial adsorptions of molecular oxygen are less probable, as no bound states are found in this case. Only after dissociation of O₂ is atomic oxygen diffusion through the surface possible. The O 2p orbitals are found to hybridize with U 5f bands, and some of the U 5f electrons become more localized. A significant charge transfer from the first layer of the uranium surface to the oxygen atoms is found to occur, making the bonding partly ionic. For the most favored site, the dissociative chemisorption energy is ～9.5 eV, which indicates a strong reaction of uranium surface with oxygen. Spin polarization does not have a significant effect on the chemisorption process. For most of the sites and approaches, chemisorption configurations are almost same for both spin‐polarized and non‐spin‐polarized cases. For the most favored chemisorption sites of oxygen on uranium, paramagnetic adsorption is slightly stronger, by 0.304 eV, compared to magnetic adsorption. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Interlocking inorganic screw helices: synthesis,structure, and magnetism of the novel framework uranium orthothiophoshates A11U7(PS4)13 (A = K,Rb)

The novel quaternary uranium thiophosphate K11U7(PS4)13 has been synthesized by reacting uranium metal, K2S, S, and P2S5 at 700 degrees C in an evacuated silica tube. The crystal structure was determined by single crystal X-ray diffraction techniques. K11U7(PS4)13 crystallizes in the tetragonal space group I42d (a = 32.048(2) A, c = 17.321(1) A, Z = 8). The structure contains a tunnel framework composed of eight interlocking uranium U7(PS4)13 screw helices, with alkali metal cations residing inside the framework channels. The uranium atoms are coordinated in a bi- or tricapped trigonal prismatic fashion. The screw helices are built up from uranium atoms interconnected by PS4 tetrahedral units. Magnetic susceptibility measurements indicate modified Curie-Weiss-type behavior between 300 and 70 K, with an effective magnetic moment of 2.54 microB per U atom at room temperature and C = 3.78, theta = -14.54, chi 0 = 0.01. The isostructural compound Rb11U7(PS4)13 (a = 32.1641(11) A, c = 17.7244(9) A, Z = 8) was prepared by heating a mixture of the formal composition UPS5 in eutectic LiCl/RbCl melts at 700 degrees C.     

Simultaneous determination of U and Th by delayed fission neutron technique based on neutron generator

A method for simultaneous determination of uranium and thorium based on the deviation of their fission cross-section curves has been developed. Using a D-T neutron generator two different neutron spectra were produced with and without moderator around the target. The detection limits were found to be 0.044 mg and 0.25 mg in the presence of a moderator, while for fast neutrons 0.017 mg and 0.037 mg for uranium and thorium, respectively.This work was supported in part by the Ministry of Higher Education and the Hungarian Academy of Sciences.     

Individual determination of uranium and plutonium in a single aliquot

Studies on the individual potentiometric determination of uranium and plutonium in a single aliquot have been initiated recently in our laboratory. It was required to adapt the reported procedures (for the precise determination of uranium and plutonium individually when present together in a sample) at various stages to make them suitable for the successive application of the procedures to the same aliquot. Two alternative schemes are proposed in the present work. In the first, plutonium is determined by HClO₄ oxidation followed by the determination of total uranium and plutonium by Zn(Hg) reduction. In the second, plutonium is determined by AgO oxidation following the determination of total uranium and plutonium by Zn(Hg) reduction. Amount of uranium is computed in both cases from the difference of two determinations. Precision for the assay of plutonium and uranium was found to be ±0.25% and ±0.35%, respectively, at milligram levels.