280 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
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
Investigation of a Pt containing washcoat on SiC foam for hydrogen combustion applications
A commercial Pt based washcoat, used for catalytic methane combustion, was studied supported on a commercial SiC foam as catalytic material (Pt/SiC) for catalytic hydrogen combustion (CHC). Structural and chemical characterization was performed using Electron Microscopy, X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS). The reaction was monitored following water concentration by Fourier Transform Infrared spectra (FTIR). The FTIR method was compared with H2 detection by Gas Cromatography (GC) and has shown to be adequate to study the kinetics of the CHC reaction in steady state under our experimental conditions (very lean 1% (v/v) H2/air mixtures). The catalyst is composed of 5â20 nm disperse Pt nanoparticles decorating a mixture of high surface area Al2O3 and small amounts of ceria supported on the SiC foam which also contains alumina as binder. The Pt/SiC catalytic material has demonstrated to be active enough to start up the reaction in a few seconds at room temperature. The material has been able to convert at least 18.5 Lhydrogen minâ1 gPtâ1 at room temperature in conditions of excess of catalyst. The Pt/SiC material was studied after use using XPS and no significant changes on Pt oxidation states were found. The material was characterized from a kinetic point of view. From the conversion-temperature plot a T50 (temperature for 50% conversion) of 34 °C was obtained. Activation energy measured in our conditions was 35 ± 1 kJ molâ1.Peer reviewe
State resolved rotational excitation cross sections and rates in H2+H2 collisions
Rotational transitions in molecular hydrogen collisions are computed. The two
most recently developed potential energy surfaces for the H2-H2 system are used
from the following works: 1) A.I. Boothroyd, P.G. Martin, W.J. Keogh, M.J.
Peterson, J. Chem. Phys., 116 (2002) 666, and 2) P. Diep, J.K. Johnson, J.
Chem. Phys., 113 (2000) 3480; ibid. 112, 4465. Cross sections for rotational
transitions 00->20, 22, 40, 42, 44 and corresponding rate coefficients are
calculated using a quantum-mechanical approach. Results are compared for a wide
range of kinetic temperatures 300 K < T < 3000 K.Comment: 9 pages, 3 figures, 3 table
A model for the formation energies of alanates and boranates
We develop a simple model for the formation energies (FEs) of alkali and
lkaline earth alanates and boranates, based upon ionic bonding between metal
cations and (AlH4)- or (BH4)- anions. The FEs agree well with values obtained
from first principles calculations and with experimental FEs. The model shows
that details of the crystal structure are relatively unimportant. The small
size of the (BH4)- anion causes a strong bonding in the crystal, which makes
boranates more stable than alanates. Smaller alkali or alkaline earth cations
do not give an increased FE. They involve a larger ionization potential that
compensates for the increased crystal bonding.Comment: 3 pages, 2 figure
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