Critical Conditions Regulating the Gelation in Macroionic Cluster Solutions.

The critical gelation conditions observed in dilute aqueous solutions of multiple nanoscale uranyl peroxide molecular clusters are reported, in the presence of multivalent cations. This gelation is dominantly driven by counterion-mediated attraction. The gelation areas in the corresponding phase diagrams all appear in similar locations, with a characteristic triangle shape outlining three critical boundary conditions, corresponding to the critical cluster concentration, cation/cluster ratio, and the degree of counterion association with increasing cluster concentration. These interesting phrasal observations reveal general conditions for gelation driven by electrostatic interactions in hydrophilic macroionic solutions.

Solid-State Transformation of Uranyl Peroxide Materials through High-Level Irradiation.

The solid-state transformation of sodium uranyl triperoxide (Na4(UO2)(O2)3·9H2O, NaUT) to sodium uranyl tricarbonate (Na4(UO2)(CO3)3) by radiolysis was observed for the first time. The exposure of NaUT to 3 MGy gamma irradiation resulted in partial breakdown of the peroxides forming a mixed peroxide and carbonate species. The effects of He-ion irradiation on NaUT were also investigated up to 225 MGy using both hydrated argon and dry argon. The complete conversion to the uranyl tricarbonate phase by 56 MGy was done using hydrated argon, while dry argon did not fully convert showing the importance of water in the system. He-ion irradiated NaUT samples all convert to the tricarbonate phase with time in air post radiation exposure. This transition was monitored via Raman spectroscopy, infrared spectroscopy (IR), and powder X-ray diffraction (PXRD) to further confirm the identity of the final product as the sodium uranyl tricarbonate, cejkaite. This transformation outlines a mechanism for the mobility of uranyl in natural environments and in the Hanford tanks.

The crystal chemistry of plutonium(IV) borophosphate.

In this work, we report the synthesis and characterization of a plutonium(IV) borophosphate, Pu(H2O)3[B2(OH)(H2O)(PO4)3] (1). The basic building unit of 1 has a B : P ratio of 2 : 3 with an equal number of BO4 and PO4 groups that assemble into 12-membered rings and take on a sheet topology due to presence of hydroxyl groups or a water molecule on one vertex of each BO4 tetrahedron. This unique borophosphate anion topology is not observed in other members of the borophosphate family; it is the plutonium(IV) metal centers, rather than borate or phosphate groups, that link the sheets to form an extended framework. The presence of boron in 1 was confirmed using single crystal X-ray diffraction, electron microprobe analysis, and infrared spectroscopy. Peaks corresponding to the tetrahedral BO45- and tetrahedral PO43- anions were all identified in the fingerprint region (500-1500 cm-1) of the infrared spectrum. Additionally, peaks in the higher wavenumber region corresponded to crystalline water and B-OH vibrations, providing further evidence for the water molecules surrounding plutonium in the structure and the protonation of the BO4 tetrahedron, respectively. This compound represents the first Pu(IV) borophosphate structure and a novel borophosphate anion topology. Furthermore, the long time-frame required for crystallization of 1 and the suspected leaching of boron from the borosilicate vial used during synthesis indicate that 1 could serve as a model for the crystalline materials that are expected to form during the corrosion of vitrified nuclear waste.

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.

Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries.

Invited for the cover of this issue is the group of Amy Hixon at the University of Notre Dame. The image depicts the newly identified structure of a PuIV oxalate sheet compared to the historically assumed structure. Read the full text of the article at 10.1002/chem.202301164.

Investigation of Radiation Effects in the Uranyl Mineral Metaschoepite.

The effects of water vapor and He ion irradiation on the alteration of particles of the uranyl hydroxide phase metaschoepite, [(UO2)8O2(OH)12](H2O)10, are determined. Raman spectra collected immediately postirradiation revealed the presence of a uranyl oxide phase structurally similar to γ-UO3 or U2O7. Short-term storage postirradiation at elevated relative humidity accelerated formation of the uranyl peroxide phase studtite, [(UO2)(O2)(H2O)2](H2O)2. Experiments examining the degradation of metaschoepite and the hydration of UO3 enabled spectral assignments and identification of reaction pathways. The results provide insights into thermal and radiolytic degradation products in both irradiated uranyl hydroxide phases and uranyl peroxide phases, which follow similar degradation pathways.

Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries.

Plutonium(IV) oxalate hexahydrate (Pu(C2 O4 )2 ⋅ 6 H2 O; PuOx) is an important intermediate in the recovery of plutonium from used nuclear fuel. Its formation by precipitation is well studied, yet its crystal structure remains unknown. Instead, the crystal structure of PuOx is assumed to be isostructural with neptunium(IV) oxalate hexahydrate (Np(C2 O4 )2 ⋅ 6 H2 O; NpOx) and uranium(IV) oxalate hexahydrate (U(C2 O4 )2 ⋅ 6 H2 O; UOx) despite the high degree of unresolved disorder that exists when determining water positions in the crystal structures of the latter two compounds. Such assumptions regarding the isostructural behavior of the actinide elements have been used to predict the structure of PuOx for use in a wide range of studies. Herein, we report the first crystal structures for PuOx and Th(C2 O4 )2 ⋅ 6 H2 O (ThOx). These data, along with new characterization of UOx and NpOx, have resulted in the full determination of the structures and resolution of the disorder around the water molecules. Specifically, we have identified the coordination of two water molecules with each metal center, which necessitates a change in oxalate coordination mode from axial to equatorial that has not been reported in the literature. The results of this work exemplify the need to revisit previous assumptions regarding fundamental actinide chemistry, which are heavily relied upon within the current nuclear field.

Electrochemistry of Uranyl Peroxide Solutions during Electrospray Ionization.

The ionization of uranyl triperoxide monomer, [(UO2)(O2)3]4- (UT), and uranyl peroxide cage cluster, [(UO2)28(O2)42 - x(OH)2x]28- (U28), was studied with electrospray ionization mass spectrometry (ESI-MS). Experiments including tandem mass spectrometry with collision-induced dissociation (MS/CID/MS), use of natural water and D2O as solvent, and use of N2 and SF6 as nebulizer gases, provide insight into the mechanisms of ionization. The U28 nanocluster under MS/CID/MS with collision energies ranging from 0 to 25 eV produced the monomeric units UOx- (x = 3-8) and UOxHy- (x = 4-8, y = 1, 2). UT under ESI conditions yielded the gas-phase ions UOx- (x = 4-6) and UOxHy- (x = 4-8, y = 1-3). Mechanisms that produce the observed anions in the UT and U28 systems are: (a) gas-phase combinations of uranyl monomers in the collision cell upon fragmentation of U28, (b) reduction-oxidation resulting from the electrospray process, and (c) ionization of surrounding analytes, creating reactive oxygen species that then coordinate to uranyl ions. The electronic structures of anions UOx- (x = 6-8) were investigated using density functional theory (DFT).

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.

Ozone-Facilitated Formation of Uranyl Peroxide in Humid Conditions.

Metaschoepite, [(UO2)8O2(OH)12](H2O)10, maintained in a high relative humidity (RH) environment with air initially transformed into an intermediate phase that subsequently was replaced by the peroxide phase studtite, [(UO2)(O2)(H2O)2](H2O)2, over the course of 42 days, as observed using Raman and infrared spectroscopy and powder X-ray diffraction. Addition of atmospheric ozone vastly increased the rate and extent of the transformation to studtite but only in a high-RH atmosphere. Owing to its strong affinity for peroxide, uranyl reacted with hydrogen peroxide as it formed and precipitated stable studtite. In this work, we provide a previously unidentified source of hydrogen peroxide and make a case for the re-examination of storage systems where the consequences of atmospheric ozone are not considered.

Radiation-Induced Solid-State Transformations of Uranyl Peroxides.

Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca2[UO2(O2)3]·9H2O reveal site-specific atomic-scale changes during the solid-state progression from a crystalline to X-ray amorphous state with increasing dose. Following γ-irradiation to 1, 1.5, and 2 MGy, the peroxide group not bonded to Ca2+ is progressively replaced by two hydroxyl groups separated by 2.7 Å (with minor changes in the unit cell), whereas the peroxide groups bonded to Ca2+ cations are largely unaffected by irradiation prior to amorphization, which occurs by a dose of 3 MGy. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H2O molecules and ionization of the peroxide O-O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO2(O2)2(OH)24-, that is ubiquitous in uranyl capsule polyoxometalates. Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. In contrast, γ-irradiation of solid Li4[(UO2)(O2)3]·10H2O results in a solid-state transformation to a well-crystallized peroxide-free uranyl oxyhydrate containing sheets of equatorial edge and vertex-sharing uranyl pentagonal bipyramids with likely Li and H2O in interlayer positions. The irradiation products of these two uranyl triperoxide monomers are compared via X-ray diffraction (single-crystal and powder) and Raman spectroscopy, with a focus on the influence of the Li+ and Ca2+ countercations. Highly hydratable and mobile Li+ yields to uranyl hydrolysis reactions, while Ca2+ provides lattice rigidity, allowing observation of the first steps of radiation-promoted transformation of uranyl triperoxide.

Ionothermal Synthesis of Uranyl Vanadate Nanoshell Heteropolyoxometalates.

Two uranyl vanadate heteropolyoxometalates (h-POMs) have been synthesized by ionothermal methods using the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-Et2PO4). The hybrid actinide-transition metal shell structures have cores of (UO2)8(V6O22) and (UO2)6(V3O12), which we designate as {U8V6} and {U6V3}, respectively. The diethyl phosphate anions of the ionic liquids in some cases terminate the core structures to form actinyl oxide clusters, and in other cases the diethyl phosphate oxyanions link these cluster cores into extended structures. Three compounds exist for the {U8V6} cluster core: {U8V6}-monomer, {U8V6}-dimer, and {U8V6}-chain. Tungsten atoms can partially substitute for vanadium in the {U6V3} cluster, which results in a chain-based structure designated as {U6V3}-W. Each of these compounds contains charge-balancing EMIm cations from the ionic liquid. These compounds were characterized crystallographically, spectroscopically, and by mass spectrometry.

Experimental and Quantum Mechanical Characterization of an Oxygen-Bridged Plutonium(IV) Dimer.

We report the synthesis and characterization of K4 {[PuCl2 (NO3 )3 ]2 (µ2 -O)}⋅H2 O, which contains the first known µ2 -oxo bridge between two PuIV metal centers. Adding to its uniqueness is the Pu-(µ2 -O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu-(µ2 -O)-Pu bridge is characterized by the mixing of s-, d-, and p-orbitals from Pu with the p-orbitals of O; the 5f-orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σPu-O-Pu and two 3c-2e πPu-O-Pu bonding orbitals and that the electron density is highly polarized on the µ2 -O. Bond topology properties analysis indicates that the Pu-(µ2 -O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.

Stability of Solid Uranyl Peroxides under Irradiation.

The effects of radiation on a variety of uranyl peroxide compounds were examined using γ-rays and 5 MeV He ions, the latter to simulate α-particles. The studied materials were studtite, [(UO2)(O2)(H2O)2](H2O)2, the salt of the U60 uranyl peroxide cage cluster, Li44K16[(UO2)(O2)(OH)]60·255H2O, the salt of U60Ox30 uranyl peroxide oxalate cage cluster, Li12K48[{(UO2)(O2)}60(C2O4)30]·nH2O, and the salt of the U24Pp12 (Pp = pyrophosphate) uranyl peroxide pyrophosphate cage cluster, Li24Na24[(UO2)24(O2)24(P2O7)12]·120H2O. Irradiated powders were characterized using powder X-ray diffraction, Raman spectroscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-vis spectroscopy. A weakening of the uranyl bonds of U60 was found while studtite, U60Ox30, and U24Pp12 were relatively stable to γ-irradiation. Studtite and U60 are the most affected by α-irradiation forming an amorphous uranyl peroxide as characterized by Raman spectroscopy and powder X-ray diffraction while U60Ox30 and U24Pp12 show minor signs of the formation of an amorphous uranyl peroxide.

Hybrid Uranyl-Phosphonate Coordination Nanocage.

We report herein a general synthetic approach for designing uranyl coordination cages. Compounds 1 and 2 are constructed through a temperature-dependent and solvent-driven self-assembly. In both cases, the synthetic strategy involves in situ phosphonate ligand condensation into a flexible pyrophosphonate ligand. This pyrophosphonate ligand formation is essential for the introduction of curvature into these compounds. In the presence of PF6- ions that are derived from hydrofluoric acid, a macrocyclic uranyl-phosphonate discrete compound, 1, whose cavity contains PF6- ions, hydronium ions, and water molecules, is obtained. When Cs+ cations are used in the synthesis, a remarkable uranyl coordination nanocage, 2, resulted. The macrocycle (1) is approximately 10.9 × 10.9 Å2 in diameter while the nanocage (2) is approximately 15.0 × 11.3 Å2 in diameter, as measured from the outer oxygen atoms of the uranyl centers. Both compounds are constructed from a UO22+ moiety, coordinated by an additional four oxygen atoms from the phosphonate group to form pentagonal bipyramidal geometry. All the compounds fluoresce at room temperature, showing characteristic vibronically coupled charge-transfer based emission.

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu16 } and {Pu22 }.

Plutonium(IV) oxide nanoclusters represent an interesting scientific problem regarding structure-function relationships and are also relevant to global concerns surrounding plutonium reprocessing, the remediation of plutonium-contaminated soils, and the storage or disposal of plutonium-containing wastes. Here we report the synthesis of five unique PuIV oxide nanoclusters containing 38, 22, or 16 metal centers and capped only with inorganic ligands, such as chlorine and water, which prevent formation of the extended PuO2 structure. The products are interrogated through single-crystal X-ray diffraction, bond valence calculations, and comparisons to other known metal-oxide nanoclusters. Of particular interest is the incorporation of hydroxide linkages into the smaller plutonium oxide nanoclusters, which underscores previous observations and hypotheses regarding the formation of plutonium polymers and colloids.

Uranyl Peroxide Cage Cluster Solubility in Water and the Role of the Electrical Double Layer.

Uranium concentrations as high as 2.94 × 105 parts per million (1.82 mol of U/1 kg of H2O) occur in water containing nanoscale uranyl cage clusters. The anionic cage clusters, with diameters of 1.5-2.5 nm, are charge-balanced by encapsulated cations, as well as cations within their electrical double layer in solution. The concentration of uranium in these systems is impacted by the countercations (K, Li, Na), and molecular dynamics simulations have predicted their distributions in selected cases. Formation of uranyl cages prevents hydrolysis reactions that would result in formation of insoluble uranyl solids under alkaline conditions, and these spherical clusters reach concentrations that require close packing in solution.

Hybrid Lanthanide-Actinide Peroxide Cage Clusters.

A cage cluster consisting of 31 uranyl and 9 Sm(3+) polyhedra self-assembles in an alkaline aqueous peroxide solution and crystallizes (U31Sm9). Trimers of Sm(3+) polyhedra are templated by µ3-η(2):η(2):η(2)-peroxide groups and link to oxo atoms of uranyl ions. Three such trimers link into a ring through uranyl hexagonal bipyramids, and these are attached through six polyhedra to a unit consisting of 21 uranyl hexagonal bipyramids to complete the cage. Luminescence spectra collected with an excitation wavelength of 420 nm reveal fine structure, which is not observed for a cluster containing only uranyl polyhedra.

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U2O7.

Recent accidents resulting in worker injury and radioactive contamination occurred due to pressurization of uranium yellowcake drums produced in the western U.S.A. The drums contained an X-ray amorphous reactive form of uranium oxide that may have contributed to the pressurization. Heating hydrated uranyl peroxides produced during in situ mining can produce an amorphous compound, as shown by X-ray powder diffraction of material from impacted drums. Subsequently, studtite, [(UO2)(O2)(H2O)2](H2O)2, was heated in the laboratory. Its thermal decomposition produced a hygroscopic anhydrous uranyl peroxide that reacts with water to release O2 gas and form metaschoepite, a uranyl-oxide hydrate. Quantum chemical calculations indicate that the most stable U2O7 conformer consists of two bent (UO2)(2+) uranyl ions bridged by a peroxide group bidentate and parallel to each uranyl ion, and a µ2-O atom, resulting in charge neutrality. A pair distribution function from neutron total scattering supports this structural model, as do (1)H- and (17)O-nuclear magnetic resonance spectra. The reactivity of U2O7 in water and with water in air is higher than that of other uranium oxides, and this can be both hazardous and potentially advantageous in the nuclear fuel cycle.

Raman spectroscopic and ESI-MS characterization of uranyl peroxide cage clusters.

Strategies for interpreting mass spectrometric and Raman spectroscopic data have been developed to study the structure and reactivity of uranyl peroxide cage clusters in aqueous solution. We demonstrate the efficacy of these methods using the three best-characterized uranyl peroxide clusters, {U24}, {U28}, and {U60}. Specifically, we show a correlation between uranyl-peroxo-uranyl dihedral bond angles and the position of the Raman band of the symmetric stretching mode of the peroxo ligand, develop methods for the assignment of the ESI mass spectra of uranyl peroxide cage clusters, and show that these methods are generally applicable for detecting these clusters in the solid state and solution and for extracting information about their bonding and composition without crystallization.