Vacancy-mediated hydrogen desorption in NaAlH4

First-principles calculations based on density functional theory are carried out to understand the mechanisms responsible for hydrogen desorption from Ti-doped sodium-alanate (NaAlH4). While the energy needed to remove a hydrogen atom from NaAlH4 with Ti substituted either at the Na site or at Al site is found to be significantly lower than that from the pristine NaAlH4, the presence of Na vacancies is shown to play an even larger role: It is not only an order of magnitude smaller than that from Ti-doped sodium-alanate, but the removal of hydrogen associated with a Na vacancy is exothermic with respect to formation of H2 molecule. Furthermore, we show that the unusual stabilization of the magic AlH3 cluster in the vacancy containing sodium-alanate is responsible for this diminished value of the hydrogen-removal energy. It is suggested that this role of vacancies can be exploited in the design and synthesis of complex light-metal hydrides suitable for hydrogen storage

Dehydrogenation from 3d-transition-metal-doped NaAlH4: Prediction of catalysts

A fundamental understanding of the role of catalysts in improving the kinetics and thermodynamics of hydrogen sorption in NaAlH4 is the key for using this material in hydrogen storage. The authors present a systematic theoretical study of energies needed to desorb hydrogen in 3dtransition metal (Sc–Cu)-doped NaAlH4. They show that Cr and Fe atoms can be far more effective catalysts than Ti in desorbing hydrogen. The role of the 3d metal atoms in improving the thermodynamics of dehydrogenation is attributed to a significant shortening of the bond length with neighboring Al atoms

On the structural and energetic properties of the hydrogen absorber Li2Mg(NH)2

The authors have performed density functional theory based calculations of several possible conformations for the crystal structure of Li2Mg(NH)2 and they confirm the α phase, resolved from both x-ray and neutron diffraction data, as the ground-state configuration. It is also found that although the N–H bond is stronger in Li2Mg(NH)2 than in Li2NH, hydrogen release from Li2Mg(NH)2/LiH mixture displays more favorable thermodynamics than that from the Li2NH∕LiH mixture. The insights gained from this seemingly counterintuitive result should prove helpful in the search for promising hydrogen storage materials

Micromechanical Properties of Injection-Molded Starch–Wood Particle Composites

The micromechanical properties of injection molded starch–wood particle composites were investigated as a function of particle content and humidity conditions. The composite materials were characterized by scanning electron microscopy and X-ray diffraction methods. The microhardness of the composites was shown to increase notably with the concentration of the wood particles. In addition,creep behavior under the indenter and temperature dependence were evaluated in terms of the independent contribution of the starch matrix and the wood microparticles to the hardness value. The influence of drying time on the density and weight uptake of the injection-molded composites was highlighted. The results revealed the role of the mechanism of water evaporation, showing that the dependence of water uptake and temperature was greater for the starch–wood composites than for the pure starch sample. Experiments performed during the drying process at 70°C indicated that the wood in the starch composites did not prevent water loss from the samples.Peer reviewe

Magnetic and electronic properties of 3d transition-metal-doped In

The magnetic and electronic properties of the transition metal (TM) (V, Cr, Mn, Fe, Co, Ni, Cu) doped In2O3 have been theoretically studied by using the density functional theory. When two TM ions are placed close to each other (TM-TM distance of about 3.4 Å), the ferromagnetic ordering is found to be the lowest-energy configuration. The only exception is Fe, which possesses a half-filled $3d$ band. However, for further separation distance of about 7.2 Å, only Co, Ni and Cu ions (having more than half-filled $3d$ band) still prefer the ferromagnetic orientation, while V, Cr, or Mn ions (having less than half-filled $3d$ band) prefer antiferromagnetic ordering. The energies of the $3d$ band for TM ions show a decrease with increasing TM atomic number. For V, Cr and Mn, the $3d$ bands are merged with the conduction band, and show less hybridization with the host valence band; while for Co, Ni and Cu, the $3d$ bands show strong hybridization with the host valence band mainly formed by the oxygen $2p$ state. In this situation, polarized holes are formed on the oxygen sites close to the TM ions. Moreover, V-doped In2O3 is found to meet the requirements for a strong donor-mediated ferromagnetism

Tuning magnetic properties of In

The electronic structure and magnetic properties of In2O3 with four kinds of intrinsic point defects (O vacancy, In interstitial, O interstitial, and In vacancy) have been theoretically studied using the density functional theory. The defect energy states of the O vacancy and In interstitial are close to the bottom of conduction band and act as shallow donors, while the defect energy states of the In vacancy and O interstitial are just above the top of the valence band and act as shallow acceptors. Without addition of any magnetic ions, all the hole states are completely spin polarized, while the electron states display no spin polarization. This implies that semiconducting In2O3 can display magnetic ordering, purely due to the intrinsic defects. However, the formation energies for neutral p-type defects are too high to be thermodynamically stable at reasonable temperatures. Nevertheless, it is shown that negative charging can greatly decrease the formation energies of p-type defects, simultaneously removing the local magnetic moments. We conlcude that VIn''' and OI'' will be the dominant compensating defects as In2O3 is doped with TM ions, such as Sn, Mo, V and Cr. This result is consistent with the general view that the p-type defect is a key feature to mediate ferromagnetic coupling between transition metal ions of dilute concentration in metal oxides

Structurally induced insulator-metal transition in solid oxygen: A quasiparticle investigation

International audienceStructural phase transition of solid oxygen has been investigated by using ab initio calculations based on density functional theory. We found sudden jumps in structural parameters at the transition pressure, which confirm that the epsilon (γ) phase undergoes a first-order isostructural phase transformation to the zeta (ζ) phase. In particular, this happens without any molecular dissociation. Using the GW approximation to calculate the band-gap closure under high pressure, we show that the structural transition is accompanied by an insulator-metal transition, contrary to a standard density functional calculation which predicts a metallization at a much lower pressure in the γ phase