A new adamantanecarboxylate coordination polymer: poly[[(μ3‐adamantane‐1,3‐dicarboxylato)aquadioxidouranium(VI)] monohydrate]

The title compound, {[U(C₁₂H₁₄O₄)O₂(H₂O)]·H₂O}_n, is the first actinide complex featuring adamantanecarboxylate ligands. The metal ion possesses a pentagonal–bipyramidal UO₇ coordination involving two axial oxide ligands [U—O = 1.732 (5) and 1.764 (5) Å] and five equatorial O atoms [U—O = 2.259 (5)–2.494 (4) Å] of aqua and carboxylate ligands. The latter display pseudo‐chelating and bridging coordination modes of the carboxylate groups that are responsible for the generation of the centrosymmetric discrete uranium–carboxylate [UO₂(μ‐RCOO)₂UO₂] dimers [U...U = 5.5130 (5) Å] and their connection into one‐dimensional chains. Hydrogen bonding involving two coordinated and two solvent water molecules [O...O = 2.719 (7)–2.872 (7) Å] yields centrosymmetric (H₂O)₄ ensembles and provides noncovalent linkage between the coordination chains to generate a three‐dimensional network structure.     

Single crystal growth and structural characterization of four complex uranium oxides: CaUO4, β-Ca3UO6, K4CaU3O12, and K4SrU3O12

Single crystals of complex uranium oxides, CaUO₄, β-Ca₃UO₆, K₄CaU₃O₁₂ and K₄SrU₃O₁₂ were grown from carbonate melts. The crystal structures of the four uranates were determined by single crystal X-ray diffraction. CaUO₄ crystallizes in the hexagonal space group R-3m, with lattice parameters a = 6.2570(7) Å and α = 36.04(2)°. The U⁶⁺ atom in CaUO₄ is 8-coordinate and exhibits hexagonal bipyramidal geometry with six long and two short U–O bonds, typical of a uranyl species. β-Ca₃UO₆ forms in the monoclinic space group P2₁/n, with lattice parameters a = 5.728(1) Å, b = 5.956(1) Å, c = 8.298(2) Å, and β = 90.55(3)°, and adopts a distorted double perovskite structure. K₄CaU₃O₁₂ and K₄SrU₃O₁₂ crystallize in the cubic space group Im-3m with lattice parameters a = 8.483(1) Å and a = 8.582(1) Å, respectively. In all three perovskite-type oxides, the U(VI) cation is located in an octahedral coordination environment and exhibits typical uranyl geometry with four long and two short U–O bonds.     

Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

On the basis of uranyl complexes reacting with a polypyrrolic ligand (H₄L), we explored structures and reaction energies of a series of new binuclear uranium(VI) complexes using relativistic density functional theory. Full geometry optimizations on [(UO₂)₂(L)], in which two uranyl groups were initially placed into the pacman ligand cavity, led to two minimum‐energy structures. These complexes with cation–cation interactions (CCI) exhibit unusual coordination modes of uranyls: one is a T‐shaped ( T ) skeleton formed by two linear uranyls {O_exo?U₂?O_endo→U₁(?O_exo)₂}, and another is a butterfly‐like ( B ) unit with one linear uranyl coordinating side‐by‐side to a second cis‐uranyl. The CCI in T was confirmed by the calculated longest distance and lowest stretching vibrational frequency of U₂?O_endo among the four U?O bonds. Isomer B is more stable than T , for which experimental tetrameric analogues are known. The formation of B and T complexes from the mononuclear [(UO₂)(H₂L)(thf)] ( M ) was found to be endothermic. The further protonation and dehydration of B and T are thermodynamically favorable. As a possible product, we have found a trianglelike binuclear uranium(VI) complex having a O?U?O?U?O unit.     

Uranium oxide clusters by laser desorption ionization during MALDI-TOF MS analysis of uranium(VI)

Laser desorption ionization (LDI) mode of matrix-assisted laser desorptionionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis of uranium(VI)leads to the formation of uranium oxides clusters, as with fast atom bombardment(FAB). Different uranium clusters than those with FAB were observed. Threedifferent families of formula (UO₂)_x O_y ²⁺, and two of formula (UO₂)_x O_y ²⁺ were found.     

Light Promotes the Immobilization of U(VI) by Ferrihydrite

The environmental behaviors of uranium closely depend on its interaction with natural minerals. Ferrihydrite widely distributed in nature is considered as one main natural media that is able to change the geochemical behaviors of various elements. However, the semiconductor properties of ferrihydrite and its impacts on the environmental fate of elements are sometimes ignored. The present study systematically clarified the photocatalysis of U(VI) on ferrihydrite under anaerobic and aerobic conditions, respectively. Ferrihydrite showed excellent photoelectric response. Under anaerobic conditions, U(VI) was converted to U(IV) by light-irradiated ferrihydrite, in the form of UO_2+x (x < 0.25), where •O₂⁻ was the dominant reactive reductive species. At pH 5.0, ~50% of U(VI) was removed after light irradiation for 2 h, while 100% U(VI) was eliminated at pH 6.0. The presence of methanol accelerated the reduction of U(VI). Under aerobic conditions, the light illumination on ferrihydrite also led to an obvious but slower removal of U(VI). The removal of U(VI) increased from ~25% to 70% as the pH increased from 5.0 to 6.0. The generation of H₂O₂ under aerobic conditions led to the formation of UO₄•xH₂O precipitates on ferrihydrite. Therefore, it is proved that light irradiation on ferrihydrite significantly changed the species of U(VI) and promoted the removal of uranium both under anaerobic and aerobic conditions.     

Actinide interactions with microbial chelators: the dioxobis[pyridine-2,6-bis(monothiocarboxylato)]uranium(VI) ion

The title complex, bis­(tetra­phenyl­phospho­nium) dioxobis(py­ridine-2,6-dicarbo­thio­ato-O,N,O′)­uranium(VI), (C₂₄H₂₀P)₂[UO₂(C₇H₃NO₂S₂)₂], was prepared by reacting two equivalents of ­pyridine-2,6-bis­(mono­thio­carboxyl­ate) (pdtc) with uranyl nitrate. The geometry of the eight-coordinate U atom is hexagonal bipyramidal, with the uranyl O atoms in apical positions. This is the first reported complex in which this ligand binds a metal through the O and not the S atoms. Principal bond lengths include uranyl lengths of 1.774 (2) Å, U—O distances of 2.434 (2) and 2.447 (3) Å, and two U—N distances of 2.647 (3) Å. The anion lies on an inversion centre.     

Synthesis and characterization of nanometric powders of UO2+x, (Th,U)O2+x and (La,U)O2+x

This paper describes a new way of preparing nanometric powders of uranium oxide, to fit the needs of studies on UO₂ oxidation, through the electrochemical reduction of U(VI) into U(IV). These powders can also be doped with radionuclides if necessary. The precipitation of oxides occurs in reducing and anoxic conditions. This original method makes it possible to synthesize nanometric UO₂ powders with a calibrated size, as well as the Th- and La-doped UO₂ powders with a predefined composition. The powder characterization by the X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron Microscopy shows the formation of spherical crystallites of UO_2+x, (Th,U)O_2+x and (La,U)O_2+x phases. The composition can be defined by the initial Th/(Th+U) and La/(La+U) ratios in solution and the particle size can be controlled by varying the pH.     

The first uranyl complexes with valerate ions

FT–IR spectroscopy and single‐crystal X‐ray structure analysis were used to characterize the discrete neutral compound diaquadioxidobis(n‐valerato‐κ²O,O′)uranium(VI), [UO₂(C₄H₉COO)₂(H₂O)₂], (I), and the ionic compound potassium dioxidotris(n‐valerato‐κ²O,O′)uranium(VI), K[UO₂(C₄H₉COO)₃], (II). The U^VI cation in neutral (I) is at a site of 2/m symmetry. Potassium salt (II) has two U centres and two K⁺ cations residing on twofold axes, while a third independent formula unit is on a general position. The ligands in both compounds were found to suffer severe disorder. The FT–IR spectroscopic results agree with the X‐ray data. The composition and structure of the ionic potassium uranyl valerate are similar to those of previously reported potassium uranyl complexes with acetate, propionate and butyrate ligands. Progressive lengthening of the alkyl groups in these otherwise similar compounds was found to have an impact on their structures, including on the number of independent U and K⁺ sites, on the coordination modes of some of the K⁺ centres and on the minimum distances between U atoms. The evolution of the KUO₆ frameworks in the four homologous compounds is analysed in detail, revealing a new example of three‐dimensional topological isomerism in coordination compounds of U^VI.     

Chloroheptakis(dimethyl sulfoxide)­uranium(IV) trichloride

In the title complex, [UCl(C₂H₆OS)₇]Cl₃, the uranium metal center is coordinated in a distorted bicapped trigonal prism geometry by seven O atoms from di­methyl sulfoxide ligands and by a terminal chloride ligand. Charge balance is maintained by three outer‐sphere chloride ions per uranium(IV) metal center. Principle bond lengths include U—O 2.391 (2)–2.315 (2) Å, U—Cl 2.7207 (9) Å, and average S—O 1.540 (5) Å.     

Bis(1,3‐di­phenyl­propane‐1,3‐dionato‐O,O′)(di­phenyl sulfoxide‐O)dioxouranium(VI)

In the title complex, [UO₂(dbm)₂(PhSOPh)] or [UO₂(C₁₅H₁₁O₂)(C₁₂H₁₀OS)], where dbm is 1,3‐di­phenyl­propane‐1,3‐dionate, the U atom is surrounded by seven O atoms to give a distorted pentagonal bipyramidal geometry. The U—O_uranyl and U—O_dbm distances (dbm is 1,3‐di­phenyl­propane‐1,3‐dionate) are in the ranges 1.760 (6)–1.776 (5) and 2.308 (4)–2.417 (4) Å, respectively, while the U—O_sulfoxide distance is 2.427 (4) Å.     

Tetrapotassium dicarbonato­dioxo­peroxo­uranium(VI) 2.5‐hydrate,K4[U(CO3)2O2(O2)]·2.5H2O

The title compound was obtained by reacting UO₂ powder in 2 M K₂CO₃ with hydrogen peroxide. The compound contains individual [U(CO₃)₂O₂(O₂)]⁴⁻ ions, which are linked via an extended network of K atoms and hydrogen bonding. The U atom is coordinated to two trans‐axial O atoms and six O atoms in the equatorial plane, forming distorted hexagonal bipyramids. The carbonate ligands are bound to the U center in a bidentate manner, with U—O bond distances ranging from 2.438 (5) to 2.488 (5) Å. The peroxo group forms a three‐membered ring with the U atom, with U—O bond distances of 2.256 (6) and 2.240 (6) Å. The U=O bond distances of 1.806 (5) and 1.817 (5) Å, and an O—U—O angle of 175.3 (3)° are characteristic of the linear uranyl(VI) unit.     

Coordination of uranyl(VI) carbonate species in aqueous solutions

There are very few examples in nature for U(VI) compounds with carbonate ligands other than the well known tricarbonates. Especially examples of U(VI) dicarbonato compounds are nearly completely missing. Even in aqueous solutions, the dicarbonato complex was found as a species of minorimportance only. On the basis of structural data on the ligands H₂O and carbonate as well as the available data on U(VI) coordination compounds, steric requirements of equatorial coordination are studied for aqueous solution species. A pentagonally coordinated monocarbonato species [UO₂CO₃(H₂O)₃] is found as the most likely coordination. For the dicarbonato species, hexagonally coordinated [UO₂(CO₃)₂(H₂O)₂] with D_2h symmetry is found as most probable structure. Possible causes of the instability of U(VI) dicarbonato species are discussed.     

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.     

Microwave-assisted dissolution of ceramic uranium dioxide in TBP–HNO3 complex

Microwave-assisted dissolution of ceramic uranium dioxide in tri-n-butyl phosphate (TBP)–HNO₃ complex was investigated. The research on dissolution of ceramic uranium dioxide in TBP–HNO₃ inclusion complex under microwave heating showed the efficiency of the use of this method. Nitric acid present in the inclusion complex participates both dissolution of UO₂, and oxidation of U(IV)–U(VI), the resulting UO₂(NO₃)₂ extracted with tri-n-butyl phosphate. Dissolution rate depends on both temperature of microwave dissolution process, and concentration of nitric acid present in the inclusion complex. The most intensive dissolution process is when the concentration of nitric acid ≥2 mol/L and the temperature of 120 °C. From the experimental data obtained by two kinetic models activation energies were calculated. At the average activation energy of UO₂ dissolution in TBP–HNO₃ complex equal 70 kJ/mol, and reaction order is close to one, i.e. the reaction takes place in an area close to kinetic.     

New approaches to reprocessing of oxide nuclear fuel

Dissolution of UO₂, U₃O₈, and solid solutions of actinides in UO₂ in subacid aqueous solutions (pH 0.9–1.4) of Fe(III) nitrate was studied. Complete dissolution of the oxides is attained at a molar ratio of ferric nitrate to uranium of 1.6. During this process actinides pass into the solution in the form of U(VI), Np(V), Pu(III), and Am(III). In the solutions obtained U(VI) is stable both at room temperature and at elevated temperatures (60 °C), and at high U concentrations (up to 300 mg mL^?1). Behavior of fission products corresponding to spent nuclear fuel of a WWER-1000 reactor in the process of dissolution the simulated spent nuclear fuel in ferric nitrate solutions was studied. Cs, Sr, Ba, Y, La, and Ce together with U pass quantitatively from the fuel into the solution, whereas Mo, Tc, and Ru remain in the resulting insoluble precipitate of basic Fe salt and do not pass into the solution. Nd, Zr, and Pd pass into the solution by approximately 50 %. The recovery of U or jointly U + Pu from the dissolution solution of the oxide nuclear fuel is performed by precipitation of their peroxides, which allows efficient separation of actinides from residues of fission products and iron.     

Dioxouranium Complexes with Acetylpyridine Benzoylhydrazones and Related Ligands

Acetylpyridine benzoylhydrazone and related ligands react with common dioxouranium(VI) compounds such as uranyl nitrate or [NBu₄]₂[UO₂Cl₄] to form air‐stable complexes. Reactions with 2, 6‐diacetylpyridinebis(benzoylhydrazone) (H₂L^1a) or 2, 6‐diacetylpyridinebis(salicylhydrazone) (H₂L^1b) give yellow products of the composition [UO₂(L¹)]. The neutral compounds contain doubly deprotonated ligands and possess a distorted pentagonal‐bipyramidal structure. The hydroxo groups of the salicylhydrazonato ligand do not contribute to the complexation of the metal. The equatorial coordination spheres of the complexes can be extended by the addition of a monodentate ligand such as pyridine or DMSO. The uranium atoms in the resulting deep‐red complexes have hexagonal‐bipyramidal coordination environments with the oxo ligands in axial positions. The sterical strains inside the hexagonal plane can be reduced when two tridentate benzoylhydrazonato ligands are used instead of the pentadentate 2, 6‐diacetylpyridine derivatives. Acetylpyridine benzoylhydrazone (HL²) and bis(2‐pyridyl)ketone benzoylhydrazone (HL³) deprotonate and form neutral, red [UO₂(L)₂] complexes. The equatorial coordination spheres of these complexes are puckered hexagons. X‐ray diffraction studies on [UO₂(L^1a)(pyridine)], [UO₂(L^1b)(DMSO)], [UO₂(L²)₂] and [UO₂(L³)₂] show relatively short U—O bonds to the benzoylic oxygen atoms between 2.328(6) and 2.389(8) Å. This suggests a preference of these donor sites of the ligands over their imino and amine functionalities (U—N bond lengths: 2.588(7)—2.701(6) Å ).     

X‐ray photoreduction of U(VI)‐bearing compounds

During XPS analysis, the soft X‐ray‐induced reduction of metals such as Cr(VI) and Ce(IV) in oxides has been reported in the literature and some mechanisms have been proposed to explain this phenomenon. The reduction of U(VI) by the beam during X‐ray Photoelectron Spectroscopy has been already reported in the literature but only for U(VI) sorbed or precipitated onto solids with reducing properties (as micas or pyrites) for whose Fe(II) can also induce the reduction of U(VI), or onto TiO₂ whose the photocatalytic properties are well known. The objective of this paper is to investigate the effects of X‐ray beam on U(VI) bulk compounds (UO₃, UO₂(OH)₂, (UO₂)₂SiO₄, UO₂(CH₃COO)₂ and UO₂C₂O₄). Successive U4f, U5f, C1s XPS spectra were recorded and compared as a function of the irradiation time. The XPS photoreduction of U(VI) into U(IV) is only observed for uranyl compounds containing organic matter (uranyl acetate and uranyl oxalate). Considering the evolution of the C1s signal during the X‐ray irradiation, a significant decrease of the C ? O component simultaneously to the U(VI) reduction is observed, which suggests a desorption of CO or other volatile organic products from the solid surface. All these results on U(VI) bulk compounds indicate the important role of organic carbon species in the photoreduction process and to explain these observations, a photoreduction mechanism has been suggested. Copyright © 2010 John Wiley & Sons, Ltd.     

Filling the equatorial garland of uranyl ion: its content and limitations

Crystal structure determinations on the uranyl ion complexes [H₂N(CH₃)₂]₂[UO₂(bpdc)₂], (1), (bpdc?=?2,2′-bipyridine-3,3′-dicarboxylate), [pyH]₂[UO₂(btfac)(NO₃)₂](NO₃), (2), (btfac?=?1-phenyl-4,4,4-trifluorobutane-1,3-dionate), [H₂dabco][UO₂(nta)]₂·3H₂O, (3), (dabco?=?1,4-diazabicyclo[2.2.2]octane; nta?=?nitrilotriacetate) and [Ni(cyclam)UO₂(edta)]^.2H₂O, (4), (cyclam?=?1,4,8,11-tetrazacyclotetradecane; edta?=?ethylenediaminetetraacetate) have provided further examples of U(VI) in tetragonal-, pentagonal and hexagonal-bipyramidal coordination environments. Consideration of each structure within the context of those of known relatives has been used to assess the influence of factors in addition to repulsions within the primary coordination sphere on the equatorial coordination number of U(VI).

     

Characterization of dry tube location in KAMINI reactor towards the development of k0-based IM-NAA

Polycarboxylic acid acts as hole scavenger and chelating agent, which is essential for the photocatalytic removal of multivalent metal ions. The photocatalytic uranium removal, role of chelating hole scavenger citric acid (CA), and removal mechanism were investigated in a TiO₂ suspension system. The results show that chelating agent CA is an efficient hole scavenger. The maximum removal efficiency of U(VI) reaches up to 98.6%. The uranium-bearing precipitates contains Na[(UO₂)(Cit)], UO₂, or UO₄·2H₂O. The mechanisms for the photocatalytic removal of U(VI) and the role of CA are discussed. These results suggest that proper chelating hole scavengers can promote and regulate the photocatalytic removal of multivalent metal ions.

     

UO2, NpO2 and PuO2 preparation in aqueous nitrate solutions in the presence of hydrazine hydrate

It was established that heating to 90 °C of nitrate solutions of U, Np and Pu in the presence of hydrazine hydrate results in the formation of hydrated dioxides of these elements. On ignition under inert or reducing conditions in the temperature range of 280–800 °C hydrated uranium dioxide transmogrify into crystalline UO₂. On ignition in air atmosphere UO₂·nH₂O turns into UO₃ at 440 °C and into U₃O₈ at 570–800 °C. It was shown that thermolysis of the solution containing a mixture of uranium, neptunium and plutonium nitrates at 90 °C in the presence of hydrazine hydrate allows one to prepare hydrated dioxides (U, Np, Pu)O₂·nH₂O which on heating to ~300 °C transmogrify into crystalline product of UO₂, NpO₂ and PuO₂ solid solution. The technique of preparation of solid solutions of U and Pu dioxides is very promising as simple and effective method of production of MOX-fuel for.