The increasing demand for clean energy sources that do not add more carbon dioxide and other pollutants to the environment has resulted in increased attention worldwide to the possibilities of a "hydrogen economy" as a long-term solution for a secure energy future based on potentially renewable resources. [1][2][3] Some of the greatest challenges are the discovery and development of new on-board hydrogen-storage materials and catalysts for fuel-cell-powered vehicles. New materials that store both high gravimetric (! 90 gm H 2 kg À1 ) and high volumetric (! 82 gm H 2 L À1 ) densities of hydrogen that can be delivered at temperatures between À20 and 85 8C are needed by the year 2015. [4] The volumetric constraints eliminate from consideration pressurized hydrogen systems and guide towards the development of solid storage materials. [5] There are several broad classes of solid hydrogenstorage materials that are currently being investigated as potential on-board storage materials: 1) metal materials, hydrides (e.g., MgH 2 ), [6] imides (e.g., LiNH 2 ), [7] and organic frameworks (e.g., Zn 4 O(1,4-benezenedicarboxylate)), [8] 2) complex hydrides (e.g., NaAlH 4 ), [9] and 3) carbon materials (e.g., carbon nanofibers, [10] single-wall carbon nanotubes). [11] The most thoroughly studied complex hydride, NaAlH 4 , has been shown to release hydrogen at 110 8C when doped with Ti; [12] however, the kinetics are very slow and hydrogen-storage densities are too low (56 gm H 2 kg À1 ) to meet long-term targets. The temperatures for H 2 release from carbon materials are too low, and the reported storage densities are controversial. [13] The hydrolysis of metal hydrides is being explored, but the unfavorable thermodynamics for regeneration of the spent material prevents their widespread application. For example, the reaction NaBH 4 +4 H 2 O!NaB(OH) 4 +4 H 2 is exothermic by À250 kJ mol À1 . Reaction enthalpy for hydrogen loss is an important property since near-thermoneutral thermodynamics will be critical for materials for reversible H 2 storage. To date, few of these materials meet the long-term gravimetric requirements and provide rapid hydrogen release at temperatures between À20 and 85 8C; thus, new materials and novel approaches are needed. Herein we show that the kinetics of hydrogen release are significantly enhanced at low temperatures for a new hybrid material, ammonia borane infused in nanoporous silica, and that the hydrogen purity is increased. These findings suggest that hydrogen-rich materials infused in nanoscaffolds offer a most promising approach to on-board hydrogen storage.Chemical hydrogen-storage materials that release H 2 by thermolysis without generating CO 2 may offer an attractive alternative to other systems studied. For example, the NH x BH x family of compounds [14] should provide favorable gravimetric densities of 245, 196, 140, and 75 gm H 2 kg À1 for x = 4, 3, 2, and 1, respectively. As the NB unit is isoelectronic with CC, these materials are viewed as inorganic analogues of hydrocarbons. Howeve...
adsorption by ASW films grown with 0 5 20' Bruce D. Kay? was similar to adsorption by a cwstalline ice film. However, for 0 > 30°, the amount of N,The morphology of amorphous solid water grown by vapor deposition was adsorbed by the ASW increased markedly, found t o depend strongly on the angular distribution of the water molecules reaching a maximum near 0 = 70'. At the incident from the gas phase. sternati tic variation of the incident angle during maximum, the ASW films adsorbed more than deposition using a collimated beam of water led to the growth of nonporous 20 times the amount of N, adsorbed by a t o highly porous amorphous solid water. The physical and chemical properties
The adsorption of N2 was used to investigate the porosity/morphology of thin films of amorphous solid water. Molecular beams were used to vapor deposit amorphous solid water films on a Pt(111) crystal at a variety of incident growth angles. The amount of N2 adsorbed by the amorphous solid water depends very sensitively on the growth angle and thermal history of the film. For normal and nearly normal incidence growth, the water films are relatively dense and smooth and adsorb only a small amount of N2. For larger growth angles, the films are porous and adsorb large quantities of N2 with apparent surface areas as high as ∼2700 m2/g. The physical and chemical properties of amorphous solid water are of interest because of its presence in astrophysical environments. The observations have important implications for laboratory studies which use vapor deposited amorphous solid water films as analogs for astrophysical icy bodies such as comets.
The index of refraction and thickness of amorphous solid water (ASW) films are determined using laser optical interferometry. From the film thickness, the density of ASW can be calculated directly since the molecular beam flux and the H2O condensation coefficient are both known. From the index of refraction the ASW density can also be determined using the Lorentz–Lorenz relationship. The densities determined via both methods agree within experimental uncertainty. For films deposited at 22 K using a collimated molecular beam, the index of refraction and density decrease monotonically as the deposition angle is varied from normal to oblique incidence. At normal incidence the films have an index of refraction of 1.285 and are presumed to be fully dense (0.94 g/cm3). At glancing incidence (86°) the film has a refractive index of 1.05 and a density of 0.16 g/cm3, indicating a porosity exceeding 80%. The angle-dependent film density is in semiquantitative agreement with the results of ballistic deposition simulations of ASW film growth.
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