RESUMO
Solid state materials possessing the ability for fast ionic diffusion of hydrogen have immense appeal for a wide range of energy-related applications. Ionic hydrogen transport research is dominated by proton conductors, but recently a few examples of hydride ion conductors have been observed as well. Barium hydride, BaH2, undergoes a structural phase transition around 775 K that leads to an order of magnitude increase in the ionic conductivity. This material provides a prototypical system to understand hydride ion diffusion and how the altered structure produced by the phase transition can have an enormous impact on the diffusion. We employ quasielastic and inelastic neutron scattering to probe the atomic scale diffusion mechanism and vibrational dynamics of hydride ions in both the low- and high-temperature phases. Jump lengths, residence times, diffusion coefficients, and activation energies are extracted and compared to the crystal structure to uncover the diffusion pathways. We find that the hydrogen jump distances, residence times, and energy barriers become reduced following the phase transition, allowing for the efficient conduction of hydride ions through a series of hydrogen jumps of length L = 3.1 Å.
RESUMO
Hydrogen desorption from borohydrides is often accompanied by the release of diborane. The amount of diborane released as a byproduct during the decomposition of borohydrides scales inversely with the borohydride stability, which in turn depends on the electronegativity of the corresponding cation. We present a model based on the difference between the symmetric and asymmetric assembly of B(2)H(6) units at the surface. The origin of this reaction is the degree of distortion of the BH(4)(-) anions in the bulk, hitherto depending on the degree of ionization of the cation. A practical measure of the distortion is the range in which the stretching vibration modes appear, which is the difference in the energy of the stretching vibrations of hydrogen atoms with maximum different bonding lengths (Badger's rule). We propose from this relation that the diborane released from the surface of the relatively unstable LiZn(2)(BH(4))(5) is formed from a recombination of BH(2)(δ+) and BH(4)(δ-) units. Ultra high vacuum mass spectroscopy measurements support the presented model and clarify the decomposition of stable borohydrides, such as LiBH(4). The sublimation of borohydrides in UHV competes with their decomposition.
RESUMO
The hydrogen storage properties of Fe(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and an oxidized analog, Fe(2)(O(2))(dobdc), have been examined using several complementary techniques, including low-pressure gas adsorption, neutron powder diffraction, and inelastic neutron scattering. These two metal-organic frameworks, which possess one-dimensional hexagonal channels decorated with unsaturated iron coordination sites, exhibit high initial isosteric heats of adsorption of -9.7(1) and -10.0(1) kJ mol(-1), respectively. Neutron powder diffraction has allowed the identification of three D(2) binding sites within the two frameworks, with the closest contacts corresponding to Fe-D(2) separations of 2.47(3) and 2.53(5) Å, respectively. Inelastic neutron scattering spectra, obtained from p-H(2) (para-H(2)) and D(2)-p-H(2) mixtures adsorbed in Fe(2)(dobdc), reveal weak interactions between two neighboring adsorption sites, a finding that is in opposition to a previous report of possible 'pairing' between neighboring H(2) molecules.
RESUMO
Employing femtosecond IR pump-probe and 2D spectroscopy, we measure the vibrational dynamics of LiBH(4) and several of its deuterium isotopomers. We find that the vibrational lifetime of various BH and BD stretching modes uniformly is approximately 1.5 ps for all BH(4-x)D(x)(-) units (0
