Sorption and desorption properties of a CaH2/MgB2/CaF2 reactive hydride composite as potential hydrogen storage material

The hydrogenation behavior of 3CaH₂+4MgB₂+CaF₂ composite was studied by manometric measurements, powder X-ray diffraction, differential scanning calorimetry and attenuated total reflection infrared spectroscopy. The maximum observed quantity of hydrogen loaded in the composite was 7.0 wt%. X-ray diffraction showed the formation of Ca(BH₄)₂ and MgH₂ after hydrogenation. The activation energy for the dehydrogenation reaction was evaluated by DSC measurements and turns out to be 162±15 kJ mol⁻¹ H₂. This value decreases due to cycling to 116±5 kJ mol⁻¹ H₂ for the third dehydrogenation step. A decrease of ca. 25–50 °C in dehydrogenation temperature was observed with cycling. Due to its high capacity and reversibility, this composite is a promising candidate as a potential hydrogen storage material.     

Probing the transition from hydrophilic to hydrophobic solvation with atomic scale resolution

Picosecond and femtosecond X-ray absorption spectroscopy is used to probe the changes of the solvent shell structure upon electron abstraction of aqueous iodide using an ultrashort laser pulse. The transient L(1,3) edge EXAFS at 50 ps time delay points to the formation of an expanded water cavity around the iodine atom, in good agreement with classical and quantum mechanical/molecular mechanics (QM/MM) molecular dynamics (MD) simulations. These also show that while the hydrogen atoms pointed toward iodide, they predominantly point toward the bulk solvent in the case of iodine, suggesting a hydrophobic behavior. This is further confirmed by quantum chemical (QC) calculations of I(-)/I(0)(H(2)O)(n=1-4) clusters. The L(1) edge sub-picosecond spectra point to the existence of a transient species that is not present at 50 ps. The QC calculations and the QM/MM MD simulations identify this transient species as an I(0)(OH(2)) complex inside the cavity. The simulations show that upon electron abstraction most of the water molecules move away from iodine, while one comes closer to form the complex that lives for 3-4 ps. This time is governed by the reorganization of the main solvation shell, basically the time it takes for the water molecules to reform an H-bond network. Only then is the interaction with the solvation shell strong enough to pull the water molecule of the complex toward the bulk solvent. Overall, much of the behavior at early times is determined by the reorientational dynamics of water molecules and the formation of a complete network of hydrogen bonded molecules in the first solvation shell.     

Chern-Simons invariants of 3-manifolds decomposed along tori and the circle bundle over the representation space ofT 2

We describe a cut-and-paste method for computing Chern-Simons invariant of flatG-connections on 3-manifolds decomposed along tori, especially forG=SU(2) andSL(2,C). We use this method to make computations ofSU(2) Chern-Simons invariants of graph manifolds which generalize Fintushel and Stern's computations for Seifert-fibered spaces. We also use this technique to give a simple derivation of a formula of Yoshida relating the flatSL(2,C) Chern-Simons invariant of the holonomy representation to the volume and the metric Chern-Simons invariant for cusped hyperbolic 3-manifolds.     

Neue Oxocuprate(I): Zur Kenntnis von CsCuO

New Oxocuprates(I): On CsCuO New obtained is CsCuO, powder as well as transparent single crystals yellow greenish. The orthorhombic structure (Ama2, a = 5.086(1), b = 10.238(2), c = 5.899(1) Å, Z = 4, four-circle-diffractometer data, R = 9.6% for 379 hkl, MoKα) is characterized by “zick-zack”-chains [CuO_2/2] parallel to [100], which are not tied together by additional Cu⁺. Motifs of mutual adjunction, Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Catalytic mechanism of transition-metal compounds on Mg hydrogen sorption reaction

The catalytic mechanisms of transition-metal compounds during the hydrogen sorption reaction of magnesium-based hydrides were investigated through relevant experiments. Catalytic activity was found to be influenced by four distinct physico-thermodynamic properties of the transition-metal compound: a high number of structural defects, a low stability of the compound, which however has to be high enough to avoid complete reduction of the transition metal under operating conditions, a high valence state of the transition-metal ion within the compound, and a high affinity of the transition-metal ion to hydrogen. On the basis of these results, further optimization of the selection of catalysts for improving sorption properties of magnesium-based hydrides is possible. In addition, utilization of transition-metal compounds as catalysts for other hydrogen storage materials is considered.     

Nb2O5 "pathway effect" on hydrogen sorption in Mg

In the present work we investigate the hydrogen sorption mechanism in a MgH(2)/Nb(2)O(5) composite and analyze why Nb(2)O(5) could strongly improve hydrogen sorption kinetics in magnesium. Hereby we make use of the fact that Nb(2)O(5) nanoparticles are able to reduce the milling time significantly with the achievement of excellent sorption kinetics, and can so exclude effects occurring at long-term milling that make difficult the study of the mechanism. On the basis of extensive chemical, crystalline, and microstructural characterization of the MgH(2)/Nb(2)O(5) nanopowder system, a "pathway model" is proposed, which explains the kinetic hydrogen sorption improvement by a formation of pathways of niobium oxide species with lower oxidation state that facilitate the hydrogen transport into the sample. This mechanism is shown to be supported by additional oxidation experiments, which indicate increased oxygen diffusion through these pathways.     

“Isomorphous” phases in nanodispersed powders of rare-earth oxides

Using x-ray diffraction, a structural state consisting of two “isomorphous” phases was revealed in nanocrystalline powders of simple oxides Re ₂O₃ (Re = Eu, Gd, La, Lu) and Y₃Ga₅O₁₂ prepared by solvent thermolysis from simple-oxide solutions followed by annealing of obtained precursors at elevated temperatures. A model is proposed explaining such two-phase states in terms of the excess energy of nanograin surface layers which causes the formation of a surface phase isomorphous to the core phase having a smaller lattice parameter. Analogous two-phase states were also obtained in microcrystalline LuBO₃ and Eu₂(MoO₄)₃ powders subjected to long-term grinding.