330 research outputs found
Role of Li_2B_(12)H_(12) for the Formation and Decomposition of LiBH_4
By in situ X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy, the role
of Li_2B_(12)H_(12) for the sorption of LiBH_4 is analyzed. We demonstrate that Li_2B_(12)H_(12) and an
amorphous Li_2B_(10)H_(10) phase are formed by the reaction of LiBH_4 with diborane (B_2H_6) at 200 °C.
Based on our present results, we propose that the Li -2B - (12)H_(12) formation in the desorption of LiBH_4 can
be explained as a result of reaction of diborane and LiBH_4. This reaction of the borohydride with
diborane may also be observed for other borohydrides, where B_(12)H_(12) phases are found during
decomposition
Model for the hydrogen adsorption on carbon nanostructures
The hydrogen sorption capacity of carbon nanostructures was for several years a very controversial subject. Theoretical models have been published demonstrating a great potential for a large hydrogen sorption capacity of carbon nanostructures. Here we present a simple empirical model where condensation of hydrogen as a monolayer at the surface of nanotubes as well as bulk condensation in the cavity of the tube is assumed. The maximum potential amount of hydrogen absorbed according to the model was calculated to be 2.28Ă10-3massâ%âS[m2g-1]=3.0massâ% for the adsorption of a monolayer hydrogen at the surface. The condensation of hydrogen in the cavity of the tube leads to a potential absorption for single wall nanotubes starting at 1.5massâ% and increasing with the diameter of the tubes. The experimentally measured hydrogen capacity of the nanotube samples correlates with the B.E.T. specific surface area. The slope of the linear relationship is 1.5Ă10-3massâ%/m2g-1. Therefore, the extrapolated maximum discharge capacity of a carbon sample is 2massâ%. Furthermore, it can be concluded, that the hydrogen sorption mechanism is related to the surface of the sample, i.e. a surface adsorption proces
First-principles study on the intermediate compounds of LiBH
We report the results of the first-principles calculation on the intermediate
compounds of LiBH. The stability of LiBH and LiBH has been examined with the ultrasoft pseudopotential method based on
the density functional theory. Theoretical prediction has suggested that
monoclinic LiBH is the most stable among the candidate
materials. We propose the following hydriding/dehydriding process of LiBH
via this intermediate compound : LiBHLiBH LiH HLiH B H. The hydrogen content and enthalpy of the first
reaction are estimated to be 10 mass% and 56 kJ/mol H, respectively, and
those of the second reaction are 4 mass% and 125 kJ/mol H. They are in good
agreement with experimental results of the thermal desorption spectra of
LiBH. Our calculation has predicted that the bending modes for the
-phonon frequencies of monoclinic LiBH are lower than
that of LiBH, while stretching modes are higher. These results are very
useful for the experimental search and identification of possible intermediate
compounds.Comment: 7 pages, 5 figures, submitted to PR
Electronic structure and optical properties of lightweight metal hydrides
We study the electronic structures and dielectric functions of the simple
hydrides LiH, NaH, MgH2 and AlH3, and the complex hydrides Li3AlH6, Na3AlH6,
LiAlH4, NaAlH4 and Mg(AlH4)2, using first principles density functional theory
and GW calculations. All these compounds are large gap insulators with GW
single particle band gaps varying from 3.5 eV in AlH3 to 6.5 eV in the MAlH4
compounds. The valence bands are dominated by the hydrogen atoms, whereas the
conduction bands have mixed contributions from the hydrogens and the metal
cations. The electronic structure of the aluminium compounds is determined
mainly by aluminium hydride complexes and their mutual interactions. Despite
considerable differences between the band structures and the band gaps of the
various compounds, their optical responses are qualitatively similar. In most
of the spectra the optical absorption rises sharply above 6 eV and has a strong
peak around 8 eV. The quantitative differences in the optical spectra are
interpreted in terms of the structure and the electronic structure of the
compounds.Comment: 13 pages, 10 figure
Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon
Methane adsorption at high pressures and across a wide range of temperatures was investigated on the surface of three porous carbon adsorbents with complementary structural properties. The measured adsorption equilibria were analyzed using a method that can accurately account for nonideal fluid properties and distinguish between absolute and excess quantities of adsorption, and that also allows the direct calculation of the thermodynamic potentials relevant to adsorption. On zeolite-templated carbon (ZTC), a material that exhibits extremely high surface area with optimal pore size and homogeneous structure, methane adsorption occurs with unusual thermodynamic properties that are greatly beneficial for deliverable gas storage: an enthalpy of adsorption that increases with site occupancy, and an unusually low entropy of the adsorbed phase. The origin of these properties is elucidated by comparison of the experimental results with a statistical mechanical model. The results indicate that temperature-dependent clustering (i.e., reduced configurations) of the adsorbed phase due to enhanced lateral interactions can account for the peculiarities of methane adsorbed on ZTC
Structural and optical properties of Mg<sub>x</sub>Al<sub>1-x</sub>H<sub>y</sub> gradient thin films: a combinatorial approach
The structural, optical and dc electrical properties of MgxAl1-x (0.2â€xâ€0.9) gradient thin films covered with Pd/Mg are investigated before and after exposure to hydrogen. We use hydrogenography, a novel high-throughput optical technique, to map simultaneously all the hydride forming compositions and the kinetics thereof in the gradient thin film. Metallic Mg in the MgxAl1-x layer undergoes a metal-to-semiconductor transition and MgHâ is formed for all Mg fractions x investigated. The presence of an amorphous Mg-Al phase in the thin film phase diagram enhances strongly the kinetics of hydrogenation. In the Al-rich part of the film, a complex H-induced segregation of MgHâ and Al occurs. This uncommon large-scale segregation is evidenced by metal and hydrogen profiling using Rutherford backscattering spectrometry and resonant nuclear analysis based on the reaction ÂčH(Âčâ”N,αγ)ÂčÂČC. Besides MgHâ, an additional semiconducting phase is found by electrical conductivity measurements around an atomic [Al]/[Mg] ratio of 2 (x=0.33). This suggests that the film is partially transformed into Mg(AlHâ)â at around this composition
Functionalised metal-organic frameworks: a novel approach to stabilising single metal atoms
We have investigated the potential of metal-organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr). Our Transmission Electron Microscopy and in-situ Raman spectroscopy results give evidence for the first time that functionalised metal-organic frameworks may support, isolate and stabilise single atoms of palladium. Using Thermal Desorption Spectroscopy we were able to evaluate the proportion of single Pd atoms. Furthermore, in a combined theoretical-experimental approach, we show that the H-H bonds in a H2 molecule elongate by over 15% through the formation of a complex with single atoms of Pd. Such deformation would affect any hydrogenation reaction and thus the single atoms supported on metal-organic frameworks may become promising single atom catalysts in the future
Hydrogen Dynamics in Lightweight Tetrahydroborates
The high hydrogen content in complex hydrides such as M[AlH4]x and M[BH4]x (M = Li, Na,K, Mg, Ca) stimulated many research activities to utilize them as hydrogen storage materials. An understanding of the dynamical properties on themolecular level is important to understand and to improve the sorption kinetics. Hydrogen dynamics in complex hydrides comprise long range translational diffusion as well as localized motions like vibrations, librations or rotations. All the different motions are characterized by their specific length- and timescales. Within this review we give an introduction to the physical properties of lightweight complex hydrides and illustrate the huge variety of dynamical phenomena on selected example
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