Effective storage of electrons in water by the formation of highly reduced polyoxometalate clusters

Aqueous solutions of polyoxometalates (POMs) have been shown to have potential as high-capacity energy storage materials due to their potential for multi-electron redox processes, yet the mechanism of reduction and practical limits are currently unknown. Herein, we explore the mechanism of multi-electron redox processes that allow the highly reduced POM clusters of the form {MO3}y to absorb y electrons in aqueous solution, focusing mechanistically on the Wells–Dawson structure X6[P2W18O62], which comprises 18 metal centers and can uptake up to 18 electrons reversibly (y = 18) per cluster in aqueous solution when the countercations are lithium. This unconventional redox activity is rationalized by density functional theory, molecular dynamics simulations, UV–vis, electron paramagnetic resonance spectroscopy, and small-angle X-ray scattering spectra. These data point to a new phenomenon showing that cluster protonation and aggregation allow the formation of highly electron-rich meta-stable systems in aqueous solution, which produce H2 when the solution is diluted. Finally, we show that this understanding is transferrable to other salts of [P5W30O110]15– and [P8W48O184]40– anions, which can be charged to 23 and 27 electrons per cluster, respectively

Non-Standard Errors

In statistics, samples are drawn from a population in a data-generating process (DGP). Standard errors measure the uncertainty in estimates of population parameters. In science, evidence is generated to test hypotheses in an evidence-generating process (EGP). We claim that EGP variation across researchers adds uncertainty: Non-standard errors (NSEs). We study NSEs by letting 164 teams test the same hypotheses on the same data. NSEs turn out to be sizable, but smaller for better reproducible or higher rated research. Adding peer-review stages reduces NSEs. We further find that this type of uncertainty is underestimated by participants

Using Metal-Oxo Clusters to Expand Actinide Chemistry

A molecular approach to metal oxides allows to the study to fundamental bonding and formation behavior for such metals. Moreover, the molecular nature of such oxides or metal-oxo clusters allows the possibility of exploitation of the properties of the parent oxides. The tetravalent metals, in specific, (M=Zr, Hf, Ce, Th, U, Np, Pu) have been chemist’s choice in bottoms-up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Actinide-oxide clusters, colloids, and materials are particularly sought after and studied for 1) nuclear materials applications, 2) understanding environmental fate and transport of actinides, and 3) exploring the complex bonding behavior of open-shell f-elements. Synthesis of these metal-oxo cluster depend on controlling the hydrolysis and condensation reactions the govern oxide formation. Herein we demonstrate control over the reactions can be met by using counterions and strongly coordinating oxo-anions. As such we demonstrate three new crystal structure families, M6, M84, and M70, and how to access them. The study using three tetravalent metals (Th, U, Ce) additionally allows to probe differences between the metals in the tetravalent group

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

MIV molecular oxo-clusters of the f- and d-block (M=Zr, Hf, Ce, Th, U, Np, Pu) have been prolific in bottoms-up material design, catalysis, as well as understanding metal oxide assembly, dissolution and surface reactivity in nature and in synthesis. Here we introduce Ce70, a new CeIV wheel-shaped oxo-cluster, [CeIV(OH)36(O)64(SO4)60(H2O)10]4-, isostructural with prior-reported U70. Like U70, Ce70 crystallizes into intricate frameworks with divalent transition metal counter-cations (TMII), and also CeIV-monomer and sulfate addenda ions

Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

International audienceIsolating isomorphic compounds of tetravalent actinides (i.e., Th IV , U IV , Np IV , and Pu IV) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and Hf) and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [M IV 6O4(OH)4] 12+ building block. Prior studies have shown the predominance and coexistence of smaller species for Th IV (monomers, dimers, and hexamers) and larger species for U IV , Np IV , and Pu IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th IV (and Zr IV) in its isolated solid-phase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U2) formulated as U2(OH)2(SO4)3(H2O)4 and a monomer-linked hexamer framework (U-U6) as (U(H2O)3.5)2U6O4(OH)4(SO4)10(H2O)9. These structures are similar to those previously described for Th IV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer-hexamer phases for both Th IV (prior) and U IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U2 and U-U6 crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV-vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, and increased complexity, with increasing pH. This study describes a bridge across the first half the actinide series, highlighting U IV similarities to Th IV , in addition to the previously known similarities to the transuranic elements

Supramolecular Assembly of U(IV) Clusters and Superatoms

Superatoms are nanometer-sized molecules or particles that can form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in superlattices of quantum-dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters; acidity and the countercation. In acid, larger LnIII (Ln=La-Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln=Er-Lu &Y) promote linking of fourteen U6-clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations, and U6-clusters. Divalent transition metals (TM=MnII and ZnII), with no added acid, charge-balance and promote the fusion of 10 U6 and 10 U-monomers into a wheel–shaped cluster (U70). Dissolution of U70 in organic media reveals (by small-angle Xray scattering) that differing supramolecular assemblies are accessed, controlled by TM-linking of U70-clusters. <br /

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10] 4- , part of a larger emerging family of MIV70- materials (M=Zr, U, Ce), presents such an opportunity. We have elucidated assembly mechanisms by X-ray scattering (small-angle scattering and total scattering) of solutions and solids, as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12] 10- ) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6- and Ce62, [Ce62(OH)30(O)58(SO4)58] 14- ). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4 +, which can also be replaced by other cations, demonstrated with CeIII. Room temperature rapid assembly of both Ce70 and Ce62, respectively, by addition of Li+ and NH4 +, along with ion?exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4‑Hydroxybenzoates

Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports have focused on actinide complexation by relatively simple monocarboxylates such as amino acids, in this work we examined Th­(IV) and U­(IV) complexation by 4-hydroxybenzoic acid in water with the aim of understanding the impact that the organic backbone has on the solution and solid state structural chemistry of thorium­(IV) and uranium­(IV) complexes. Two compounds of the general formula [An₆O₄(OH)₄(H₂O)₆(4-HB)₁₂]·<i>n</i>H₂O [An = Th (<b>Th-1</b>) and U (<b>U-1</b>); 4-HB = 4-hydroxybenzoate] were synthesized via room-temperature reactions of AnCl₄ and 4-hydroxybenzoic acid in water. Solid state structures were determined by single-crystal X-ray diffraction, and the compounds were further characterized by Raman, infrared, and optical spectroscopies and thermogravimetry. The magnetism of <b>U-1</b> was also examined. The structures of the Th and U compounds are isomorphous and are built from ligand-decorated oxo/hydroxo-bridged hexanuclear units. The relationship between the building units observed in the solid state structure of <b>U-1</b> and those that exist in solution prior to crystallization as well as upon dissolution of <b>U-1</b> in nonaqueous solvents was investigated using small-angle X-ray scattering, ultraviolet–visible optical spectroscopy, and dynamic light scattering. The evolution of U solution speciation as a function of reaction time and temperature was examined. Such effects as well as the impact of the ligand on the formation and evolution of hexanuclear U­(IV) clusters to UO₂ nanoparticles compared to prior reported monocarboxylate ligand systems are discussed. Unlike prior reported syntheses of Th and U­(IV) hexamers where the pH was adjusted to ∼2 and 3, respectively, to drive hydrolysis, hexamer formation with the HB ligand appears to be promoted only by the ligand