Solvent effects on extractant conformational energetics in liquid-liquid extraction: a simulation study of molecular solvents and ionic liquids.

Extractant design in liquid-liquid extraction (LLE) is a research frontier of metal ion separations that typically focuses on the direct extractant-metal interactions. However, a more detailed understanding of energetic drivers of separations beyond primary metal coordination is often lacking, including the role of solvent in the extractant phase. In this work, we propose a new mechanism for enhancing metal-complexant energetics with nanostructured solvents. Using molecular dynamics simulations with umbrella sampling, we find that the organic solvent can reshape the energetics of the extractant's intramolecular conformational landscape. We calculate free energy profiles of different conformations of a representative bidentate extractant, n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO), in four different solvents: dodecane, tributyl phosphate (TBP), and dry and wet ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]). By promoting reorganization of the extractant molecule into its binding conformation, our findings reveal how particular solvents can ameliorate this unfavorable step of the metal separation process. In particular, the charge alternating nanodomains formed in ILs substantially reduce the free energy penalty associated with extractant reorganization. Importantly, using alchemical free energy calculations, we find that this stabilization persists even when we explicitly include the extracted cation. These findings provide insight into the energetic drivers of metal ion separations and potentially suggest a new approach to designing effective separations using a molecular-level understanding of solvent effects.

Magnetic Properties of Tetravalent Pu in the Perovskites BaPuO3 and SrPuO3.

BaPuO3 and SrPuO3 were synthesized, and their structures were refined in the orthorhombic space group Pbnm, a common distortion from the classic Pm3̅m cubic perovskite. Magnetic-susceptibility measurements, obtained as a function of temperature over the range of 1.8-320 K, exhibit temperature-dependent behavior, with evidence of long-range magnetic order at temperatures higher than their lanthanide and actinide analogues: BaPuO3 below 164(1) K and SrPuO3 below 76(1) K. Effective moments of 1.66(10)µB for BaPuO3 and 1.84(8)µB for SrPuO3 were obtained by fitting their paramagnetic susceptibilities using the Curie-Weiss law. Both are below the free-ion value of 2.68 µB expected for a Pu4+ 5I4 ground level. Ab initio wave function calculations, performed at the relativistic complete active space level including spin-orbit coupling and with an embedded cluster approach that neglects interactions between Pu centers, were used to generate embedded-cluster Pu4+ magnetic susceptibilities. The calculations agree well with experimental data at higher temperatures, providing evidence that a single-ion representation is sufficient to account for the observed paramagnetic behavior without the need to invoke charge transfer, disproportionation, strong covalent bonding, or other more complex electronic behavior.

Molecular-scale origins of solution nanostructure and excess thermodynamic properties in a water/amphiphile mixture.

The molecular and nanoscale origins of nonideality in excess thermodynamic properties are essential to understanding cosolvent mixtures, yet they remain challenging to determine. Here, we consider a binary mixture of water and an amphiphile, N,N,N',N'-tetramethylmalonamide (TMMA), which is characterized by strong hydrogen bonding between the two components and no hydrogen bonding between amphiphiles. Using molecular dynamics simulation, validated with excess volume measurements and X-ray scattering, we identify three distinct solution regimes across the composition range of the binary mixture and find that the transition between two of these regimes, marked by the water percolation threshold, is closely correlated with minima in the excess volume and excess enthalpy. Structural analysis of the simulations reveals an interplay between local interactions and solution nanostructure, determined by the relative strength of the water-water and water-amphiphile hydrogen bonding interactions. By comparison with other amphiphiles, such as linear alcohols, the relative strength of like and unlike interactions between water and amphiphile affects the relationship between thermodynamics and structural regimes. This provides insight into how molecular forces of mutual solvation interact across length scales and how they manifest in excess thermodynamic properties.

Nanoscale Critical Phenomena in a Complex Fluid Studied by X-Ray Photon Correlation Spectroscopy.

The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions, dodecane-DMDBTDMA with extracted aqueous Ce(NO_{3})_{3}. We observe good agreement with both static and dynamic scaling without the need for significant noncritical background corrections. Critical exponents agree with 3D Ising values, and the fluctuation dynamics are described by simple exponential relaxation. The form of the dynamic master curve deviates somewhat from the Kawasaki result, with a more abrupt transition between the critical and noncritical asymptotic behavior. The concepts of critical phenomena thus provide a quantitative framework for understanding the structure and dynamics of LLE systems and a path forward to new LLE processes.

Leveraging Actinide Hydrolysis Chemistry for Targeted Th and U Separations using Amidoxime-Functionalized Poly(HIPE)s.

Polymerized high internal phase emulsions (poly(HIPE)s) are porous polymer monoliths whose synthesis can easily be tailored to allow incorporation of functional units. In this work, nitrile containing poly(HIPE)s have been prepared with either acrylonitrile (AN) or 4-cyanostyrene (4CS) comonomers. Post-synthetic modification of these nitrile-containing poly(HIPE)s yields their corresponding amidoximated analogues, which were studied for actinide uptake. These amidoxime-functionalized, porous polymers were shown to adsorb 95 % Th4+ species from aqueous solution within 30 minutes. In contrast to other amidoxime containing polymers the uptake of UO2 2+ in these poly(HIPE)s is lower under similar conditions. A critical analysis of actinide separations and high-energy X-ray scattering data provides insight into the polymers' selectivity, enabled by the uptake of multinuclear Th clusters.

NpSe2 : a Binary Chalcogenide Containing Modulated Selenide Chains and Ambiguous-Valent Metal.

A new binary compound, NpSe2, possesses metal-chalcogen and chalcogen-chalcogen interactions different from those reported for other metal dichalcogenides. Its structure is incommensurately modulated and features linear Se chains and valence-ambiguous Np cations.

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium-Nitrate Example.

The influence of countercations (An+) in directing the composition of monomeric metal-ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of An+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A+ hydration enthalpies found for two related series of thorium (Th)-nitrate molecular compounds obtained by evaporating acidic aqueous Th-nitrate solutions in the presence of A+ counterions. Analyses of their chemical composition and solid-state structures demonstrate that A+ not only affects the overall solid-state packing of the Th-nitrato complexes but also influences the composition of the Th-nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A+ hydration enthalpies, such that the A+ with smaller hydration enthalpies associate with less hydrated and more anionic Th-nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of An+, opens a new avenue for the design and synthesis of targeted metal-ligand complexes.

Subtle Effects of Aliphatic Alcohol Structure on Water Extraction and Solute Aggregation in Biphasic Water/n-Dodecane.

Organic phase aggregation behavior of 1-octanol and its structural isomer, 2-ethylhexanol, in a biphasic n-dodecane-water system is studied with a combination of physical measurement, small-angle X-ray scattering (SAXS), and atomistic molecular dynamic simulations. Physical properties of the organic phases are probed following their mixing and equilibration with immiscible water phases. Studies reveal that the interfacial tension decreases as a function of increasing alcohol concentration over the solubility range of the alcohol with no evidence for a critical aggregate concentration (cac). An uptake of water into the organic phases is quantified, as a function of alcohol content, by Karl Fischer titrations. The extraction of water into dodecane was further assessed as a function of alcohol concentration via the slope-analysis method sometimes employed in chemical separations. This method provides a qualitative understanding of solute (water/alcohol) aggregation in the organic phase. The physical results are supported by analyses of SAXS data that reveals an emergence of aggregates in n-dodecane at elevated alcohol concentrations. The observed aggregate structure is dependent on the alcohol tail group geometry, consistent with surfactant packing parameter. The formation of these aggregates is discussed at a molecular level, where alcohol-alcohol and alcohol-water H-bonding interactions likely dominate the occurrence and morphology of the aggregates.

In situ studies of a platform for metastable inorganic crystal growth and materials discovery.

Rapid shifts in the energy, technological, and environmental demands of materials science call for focused and efficient expansion of the library of functional inorganic compounds. To achieve the requisite efficiency, we need a materials discovery and optimization paradigm that can rapidly reveal all possible compounds for a given reaction and composition space. Here we provide such a paradigm via in situ X-ray diffraction measurements spanning solid, liquid flux, and recrystallization processes. We identify four new ternary sulfides from reactive salt fluxes in a matter of hours, simultaneously revealing routes for ex situ synthesis and crystal growth. Changing the flux chemistry, here accomplished by increasing sulfur content, permits comparison of the allowable crystalline building blocks in each reaction space. The speed and structural information inherent to this method of in situ synthesis provide an experimental complement to computational efforts to predict new compounds and uncover routes to targeted materials by design.

A Comparison of Adsorption, Reduction, and Polymerization of the Plutonyl(VI) and Uranyl(VI) Ions from Solution onto the Muscovite Basal Plane.

X-ray scattering techniques [in situ resonant anomalous X-ray reflectivity (RAXR) and specular crystal truncation rods (CTR)] were used to compare muscovite (001) surfaces in contact with solutions containing either 0.1 mM plutonyl(VI) or 1 mM uranyl(VI) at pH = 3.2 ± 0.2, I(NaCl) = 0.1 M, as well as in situ grazing-incidence X-ray absorption near-edge structure (GI XANES) spectroscopy and ex situ alpha spectrometry. Details of the surface coverage are found to be very different. In the case of Pu, alpha spectrometry finds a surface coverage of 8.3 Pu/AUC (AUC = 46.72 Å2, the unit cell area), far in excess of the 0.5 Pu/AUC expected for ionic adsorption of PuO22+. GI XANES results show that Pu is predominantly tetravalent on the surface, and the CTR/RAXR results show that the adsorbed Pu is broadly distributed. Taken together with previous findings, the results are consistent with adsorption of Pu in the form of Pu(IV)-oxo-nanoparticles. In contrast, uranyl shows only negligible, if any, adsorption according to all methods applied. These results are discussed and compared within the context of known Pu and U redox chemistry.

Th3[Th6(OH)4O4(H2O)6](SO4)12(H2O)13: A Self-Assembled Microporous Open-Framework Thorium Sulfate.

A neutral-framework thorium oxohydroxosulfate hydrate has been isolated from aqueous solution. This microporous structure, which self-assembles without a templating agent, is built from [Th6(OH)4O4(H2O)6]12+ hexamers and thorium(IV) monomers linked through bridging sulfates. Solution conditions were chosen to enable an active competition between sulfate and hydroxide for thorium coordination. Synthetic requirements are discussed for this rare example of a thorium(IV) polynuclear complex containing mixed oxo-, hydroxo-, and sulfato-bridging moieties.

Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation.

We report the room temperature synthesis and structural characterization of a µ2-hydroxo-bridged Pu(IV) dimer obtained from an acidic nitric acid solution. The discrete Pu2(OH)2(NO3)6(H2O)4 moiety crystallized with two distinct crystal structures, [Pu2(OH)2(NO3)6(H2O)4]2·11H2O (1) and Pu2(OH)2(NO3)6(H2O)4·2H2O (2), which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(1) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridged distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent metal-ion condensation.

Aqueous hafnium sulfate chemistry: structures of crystalline precipitates.

Crystalline precipitates resulting from the hydrolysis and subsequent condensation of Hf(IV) aqueous acidic solutions at 60-95 °C are examined and compared. By varying the concentrations of the acid and sulfate source, a variety of complex hafnium-oxo-hydroxo-sulfate clusters are isolated and structures accessed. Four novel compounds were discovered, while the structures of two known compounds, an 18-mer and a planar hexamer, were updated. In total, the compounds described herein each contain one of four cluster architectures: 18-mer, 11-mer, nonamer, and planar hexamer. In addition, one compound contains small amounts of 19-mers together with 18-mers. As well as examining the individual structure of each complex cluster, we relate them to one another, as well as to the dense phases of HfO2, to gain an understanding of their formation and stability. Finally, the solution conditions under which each cluster forms are identified by plotting the crystallization regions of each cluster against acidity and sulfate concentration. Most clusters form under slightly acidic conditions, in decreasing size as the sulfate concentration is raised. The flat hexamer is the single exception; it appears to require more acidic solutions. The degree of hydroxo- versus oxo-bridges with changing solution conditions is assessed within the broader context of the condensates. Of specific interest is the identification of these products as they relate to the use of hydrolysis reactions in designing new materials.

Changing hafnium speciation in aqueous sulfate solutions: a high-energy X-ray scattering study.

The relationship of solution speciation and the structures of corresponding precipitates is examined for an aqueous Hf(4+) sulfate series. High-energy X-ray scattering (HEXS) and Raman spectroscopy data are used to probe atomic correlations in solutions. Hf(4+) in acidic perchlorate solution shows no evidence of a mononuclear metal species but instead has a peak in the pair-distribution function (PDF), generated from the HEXS data, at 3.55 Å, indicating Hf(4+)-Hf(4+) solution correlations. The peak intensity is consistent with clusters that are, on average, larger than the tetramic unit [M4(OH)8(H2O)16](8+) usually attributed to Zr(4+) and Hf(4+) solution speciation under these conditions. Addition of sulfate results in a breakup of hydroxo-bridged oligomers into sulfate-capped dimers and, for higher concentrations, Hf-sulfate monomers. The bidentate coordination mode of sulfate dominates the dissolved precursors, although it is not found in the structure of the final crystallized product, which instead is comprised of bridging-bidentate sulfate ligation. Neither the PDF patterns nor the Raman spectra show any evidence of the larger oligomers, such as the octadecameric metal clusters, found in similar Zr(4+) solutions. The oligomeric units found in solution provide insights into possible assembly routes for crystallization. In addition to expanding our understanding of synthesis science this study also reveals differences in the aqueous chemistries between Hf and Zr, two elements with ostensibly very similar chemical behavior.

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012).

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical UVI concentrations of contaminated water near mining sites. The analyses reveal that UVI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 Å from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H2O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. The presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic Zr chlorides and sulfates.

The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H2O)16](8+), generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH)26O20(H2O)23.2(SO4)12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm(-1) that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of <1 nm, often considered to be within the structurally amorphous regime.

An iron-dependent and transferrin-mediated cellular uptake pathway for plutonium.

Plutonium is a toxic synthetic element with no natural biological function, but it is strongly retained by humans when ingested. Using small-angle X-ray scattering, receptor binding assays and synchrotron X-ray fluorescence microscopy, we find that rat adrenal gland (PC12) cells can acquire plutonium in vitro through the major iron acquisition pathway--receptor-mediated endocytosis of the iron transport protein serum transferrin; however, only one form of the plutonium-transferrin complex is active. Low-resolution solution models of plutonium-loaded transferrins derived from small-angle scattering show that only transferrin with plutonium bound in the protein's C-terminal lobe (C-lobe) and iron bound in the N-terminal lobe (N-lobe) (Pu(C)Fe(N)Tf) adopts the proper conformation for recognition by the transferrin receptor protein. Although the metal-binding site in each lobe contains the same donors in the same configuration and both lobes are similar, the differences between transferrin's two lobes act to restrict, but not eliminate, cellular Pu uptake.

Plutonium(IV) cluster with a hexanuclear [Pu6(OH)4O4]12+ core.

A mixed hydroxo/oxo plutonium(IV) carboxylate resulting from the hydrolysis and condensation of Pu(IV) in an acidic aqueous solution has been isolated. The structure of Li6[Pu6(OH)4O4(H2O)6(HGly)12]Cl18·10.5H2O (1) consists of a cationic [Pu6(OH)4O4](12+) core that is decorated by glycine ligands. The synthesis, structure, and characterization of the hexanuclear unit, which represents the first example of a Pu(IV) polynuclear complex containing both hydroxo- and oxo-bridging ligands, are described herein.

Reinvestigation of Np2Se5: a clear divergence from Th2S5 and Th2Se5 in chalcogen-chalcogen and metal-chalcogen interactions.

Single crystals of Np2Se5 have been prepared through the reactions of Np and Se at 1223 K in an Sb2Se3 flux. The structure of Np2Se5, which has been characterized by single-crystal X-ray diffraction methods, crystallizes in the tetragonal space group P42/nmc. The crystallographic unit cell includes one unique Np and two Se positions. Se(1) atoms form one-dimensional infinite chains along the a and b axes with alternating intermediate Se-Se distances of 2.6489 (8) and 2.7999 (8) Å, whereas Se(2) is a discrete Se(2-) anion. Each Np is coordinated to 10 Se atoms and every NpSe10 polyhedron shares faces, edges, or vertices with 14 other identical metal polyhedra to form a complex three-dimensional structure. Np LIII-edge X-ray Absorption Near Edge Structure (XANES) measurements show a clear shift in edge position to higher energies for Np2Se5 compared to Np3Se5 (Np(3+)2Np(4+)Se(2-)5). Magnetic susceptibility measurements indicate that Np2Se5 undergoes a ferromagnetic-type ordering below 18(1) K. Above the transition temperature, Np2Se5 behaves as a paramagnet with an effective moment of 1.98(5) µB/Np, given by a best fit of susceptibilities to a modified Curie-Weiss law over the temperature range 50-320 K.

Surface-mediated formation of Pu(IV) nanoparticles at the muscovite-electrolyte interface.

The formation of Pu(IV)-oxo-nanoparticles from Pu(III) solutions by a surface-enhanced redox/polymerization reaction at the muscovite (001) basal plane is reported, with a continuous increase in plutonium coverage observed in situ over several hours. The sorbed Pu extends >70 Å from the surface with a maximum concentration at 10.5 Å and a total coverage of >9 Pu atoms per unit cell area of muscovite (0.77 µg Pu/cm(2)) (determined independently by in situ resonant anomalous X-ray reflectivity and by ex-situ alpha-spectrometry). The presence of discrete nanoparticles is confirmed by high resolution atomic force microscopy. We propose that the formation of these Pu(IV) nanoparticles from an otherwise stable Pu(III) solution can be explained by the combination of a highly concentrated interfacial Pu-ion species, the Pu(III)-Pu(IV) redox equilibrium, and the strong proclivity of tetravalent Pu to hydrolyze and form polymeric species. These results are the first direct observation of such behavior of plutonium on a naturally occurring mineral, providing insights into understanding the environmental transport of plutonium and other contaminants capable of similar redox/polymerization reactions.