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Abstract: Colloidal silica is a nanoparticulate material that could have a transformative effect on environmental risk management at nuclear legacy sites through their use in in-situ installation of injectable hydraulic barriers. In order to utilize such nanoparticulate material as a barrier, we require detailed understanding of its impact on the geochemistry of radionuclides in the environment (e.g. fission products such as Sr and Cs). Here we show, through combining leaching experiments with XAS analyses, that colloidal silica induces several competing effects on the mobility of Sr and Cs. First, cations within the colloidal silica gel compete with Sr and Cs for surface complexation sites. Second, an increased number of surface complexation sites is provided by the silica nanoparticles and finally, the elevated pH within the colloidal silica increases the surface complexation to clay minerals and the silica nanoparticles. XAS analyses show that Sr and Cs complex predominantly with the clay mineral phases in the soil through inner-sphere surface complexes (Sr) and through complexation on the clay basal surfaces at Si vacancy sites (Cs). For binary soil – colloidal silica gel systems, a fraction of the Sr and Cs complexes with the amorphous silica-like surfaces through the formation of outer-sphere surface complexes. Importantly, the net effect of nanoparticulate colloidal silica gel is to increase the retention of Sr and Cs, when compared to untreated soil and waste materials. Our research opens the door to applications of colloidal silica gel to form barriers within risk management strategies at legacy nuclear sites.

Open Access

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Abstract: Ni functionalized metal organic frameworks (MOF) are promising heterogeneous ethene dimerization catalysts. Activities comparable to or higher than Ni-aluminosilicates have been reported in literature. However, unlike the Ni-aluminosilicates, those Ni-MOFs require a large excess of co-catalyst to initiate the dimerization process and some catalysts generate polymers which lead to catalyst deactivation. Herein, we report a series of Ni(II) and 2,2′-bipyridine-5,5′-dicarboxylate (bpy) functionalized UiO-67 MOF that catalyze the ethene dimerization reaction co-catalyst free. The catalysts were active for ethene dimerization (up to 850 mg butene gcat-1 h-1) after activation at 300 °C in 10 % O2 for 360 min and subsequent exposure to flowing ethene (P(ethene) =26 bar, 250 °C) for 240 min. The catalysts yielded up to 6 % conversion with 99 % selectivity to linear 1- and 2-butenes, which formed in non-equilibrated ratios. Overall, the test data indicate that all three linear butenes are formed on a single active site, in accordance with the Cossee-Arlman mechanism. Ex situ XAS and CO FT-IR spectroscopy studies point towards Ni monomers or, plausibly, low-nuclearity Ni-multimers, docked at bpy linkers with Ni-Ni distances > 4 Å, as the main active site for the ethene dimerization reaction.

Open Access

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Abstract: A synthesis method for the preparation of mixed manganese–ruthenium oxides is presented along with a detailed characterisation of the solids produced. The use of 1 M aqueous sulfuric acid mediates the redox reaction between KRuO4, KMnO4 and Mn2+ to form ternary oxides. At reaction temperature of 100 °C the products are mixtures of α-MnO2 (hollandite-type) and β-MnO2 (rutile-type), with some evidence of Ru incorporation in each from their expanded unit cell volumes. At reaction temperature of 200 °C solid-solutions β-Mn1−xRuxO2 are formed and materials with x ≤ 0.6 have been studied. The amount of Ru included in the oxide is greater than expected from the ratio of metals used in the synthesis, as determined by elemental analysis, implying that some Mn remains unreacted in solution. Powder X-ray diffraction (XRD) shows that while the unit cell volume expands in a linear manner, following Vegard's law, the tetragonal lattice parameters, and the a/c ratio, do not follow the extrapolated trends: this anisotropic behaviour is consistent with the different local coordination of the metals in the end members. Powder XRD patterns show increased peak broadening with increasing ruthenium content, which is corroborated by electron microscopy that shows nanocrystalline material. X-ray absorption near-edge spectra show that the average oxidation state of Mn in the solid solutions is reduced below +4 while that of Ru is increased above +4, suggesting some redistribution of charge. Analysis of the extended X-ray absorption fine structure provides complementary local structural information, confirming the formation of a solid solution, while X-ray photoelectron spectroscopy shows that the surface oxidation states of both Ru and Mn are on average lower than +4, suggesting a disordered surface layer may be present in the materials.

Open Access

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Abstract: Di-iron dithiolate hydrogenase model complexes are promising systems for electrocatalytic production of dihydrogen and have therefore been spectroscopically and theoretically investigated in this study. The direct effect of ligand substitution on the redox activity of the complex is examined. In order to understand and eventually optimize such systems, we characterised both metal and ligand in detail, using element specific X-ray absorption Fe- and S-K edge XAS. The (electronic) structure of three different [Fe2S2] hydrogenase systems in their non-reduced state was investigated. The effect of one- and two-electron reduction on the (electronic) structure was subsequently investigated. The S K-edge XAS spectra proved to be sensitive to delocalization of the electron density into the aromatic ring. The earlier postulated charge and spin localization in these complexes could now be measured directly using XANES. Moreover, the electron density (from S K-edge XANES) could be directly correlated to the Fe–CO bond length (from Fe K-edge EXAFS), which are in turn both related to the reported catalytic activity of these complexes. The delocalization of the electron density into the conjugated π-system of the aromatic moieties lowers the basicity of the diiron core and since protonation occurs at the diiron (as a rate determining step), lowering the basicity decreases the extent of protonation and consequently the catalytic activity.

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Abstract: Increasing dependence on rechargeable batteries for energy storage calls for the improvement of energy density of batteries. Toward this goal, introduction of positive electrode materials with high voltage and/or high capacity is in high demand. The use of oxygen chemistry in lithium and sodium layered oxides has been of interest to achieve high capacity. Nevertheless, a complete understanding of oxygen-based redox processes remains elusive especially in sodium ion batteries. Herein, a novel P3-type Na0.67Ni0.2Mn0.8O2, synthesized at low temperature, exhibits oxygen redox activity in high potentials. Characterization using a range of spectroscopic techniques reveals the anionic redox activity is stabilized by the reduction of Ni, because of the strong Ni 3d–O 2p hybridization states created during charge. This observation suggests that different route of oxygen redox processes occur in P3 structure materials, which can lead to the exploration of oxygen redox chemistry for further development in rechargeable batteries.