Renewed interest in hydrogen storage materials has resulted in the development of Ti-doped NaAlH4. Different doping methods such as mechanical milling with powdered TiCl3, or wet doping in solvents such as tetrahydrofuran (THF), yield enhanced kinetics. Still, the location and action of the Ti dopant is an open question. In order to address titanium substitution in the bulk, we present lattice parameter measurements of crushed single crystals which were exposed to Ti during growth. Rietveld refinements suggest that the titanium does not appear to enter the bulk by this method of exposure. Therefore, reaction products are investigated by x-ray diffraction of completely reacted samples of solvent-mixed versus mechanically milled 3 NaAlH4+TiCl3. Formation of TiAl3 is observed in mechanically milled materials, but not solution mixed samples, where bonding to THF likely stabilizes Ti-based nano-clusters. The Ti in these clusters is activated by mechanical milling.

In this work, nanostructured composite materials Mg-Ni, Mg-Ni-La, Mg-Ni-Ce and Mg-LaNi5 have been synthesized using the mechanical alloying process. The new materials produced have been investigated by X-ray diffraction (XRD), TEM, SEM and EDS for their phase compositions, crystal structure, grain size, particle morphology and the distribution of the catalyst elements. Hydrogen storage capacities and the hydriding-dehydriding kinetics of the new materials have been measured at different temperatures using a Sieverts apparatus. The results show that amorphous/nanostructured composite material Mg50%-Ni50% absorbs 5.89wt% within five minutes and desorbs 4.46% hydrogen within 50 minutes at 250°C respectively. Adding 5% La into Mg-Ni composite materials reduces the starting temperature of hydrogen absorption and desorption from 200°C to 25°C which suggests the formation of unstable hydrides. The composite material Mg80%-LaNi5 20% absorbs 1.96% hydrogen and releases 1.75 wt% hydrogen at 25°C. It is observed that mechanical alloying accelerates the hydrogenation kinetics of the magnesium based materials at low temperature, but a high temperature must be provided to release the absorbed hydrogen from the hydrided magnesium based materials. It is believed the dehydriding temperature is largely controlled by the thermodynamic configuration of magnesium hydride. Doping Mg-Ni nano/amorphous composite materials with lanthanum reduces the hydriding and dehydriding temperature. Although the stability of MgH2 can not be easily reduced by ball milling alone, the results suggest the thermodynamic properties of Mg-Ni nano/amorphous composite materials can be alternated by additives such as La or other effective elements. Further investigation toward understanding the mechanism of additives will be rewarded.

In the ongoing search for promising compounds for hydrogen storage, novel porous metal-organic frameworks (MOF) have been discovered recently[1]. Well defined binding sites were deduced from inelastic neutron scattering (INS) spectroscopy of the rotational transitions of the adsorbed molecular hydrogen. In light of this discovery we performed ab initio density functional theory (DFT) calculations of the adsorption of molecular hydrogen on this class of microporous MOF to compare different adsorption sites. As a first step, we study the case of H2 adsorbed on benzene. The DFT code used, Abinit, is based on plane-waves and pseudopotentials. Different approximations for the exchange-correlation potentials were accessed for a set of relevant properties (binding energy, energetically favored configuration, distance between the adsorbents and adsorbates). In particular, theoretical rotational spectra of the adsorbed H2 were obtained that could be compared to the experimental INS spectra.

The hydrogen storage properties of carbon single-wall and multi-wall nanotubes (SWNTs and MWNTs), graphitic nanofibers, and other nanostructured carbons have recently become the subject of considerable debate. Reported capacities range from ∼ 0–60 wt%. Hot wire chemical vapor deposition (HWCVD) has recently been adapted for a continuous growth process for high-density carbon MWNTs. Multi-wall nanotube growth is optimized in 1:5 CH4:Ar at 150 Torr with reactor temperatures of 400 and 550°C for static and flowing gases, respectively. Ferrocene is employed to provide a gas-phase catalyst. Highly graphitic nanotubes can be continuously deposited with iron content as low as 15 wt% and carbon impurities below thermal gravimetric analysis detection limits. The MWNTs are simply purified to ∼99.5 wt% with minimal structural damage and with a 75 wt% yield. Hydrogen adsorption is observed for low pressures at near ambient temperatures on the as-synthesized MWNTs containing iron nanoparticles. However, no hydrogen adsorption, is observed at near ambient temperatures for the purified MWNTs or for purified MWNTs that were subsequently combined with iron micro/nano-particles via sonication. These results indicate that an intimate metal/graphitic carbon interaction is required for unanticipated hydrogen adsorption at near ambient conditions.

According to the stages of development, the hydrogen program in China can be divided into four periods since 1978. The chief activities and accomplishments in each period on hydrogen production, hydrogen processing and use of hydrogen in the form of energy are introduced. The work of consciously transforming the present energy system based upon coal-firing power plants and petroleum powered internal combustion engine vehicles into a hydrogen economy system with primary energy mainly based on renewable energies and recycling of biomass and the use of both electricity and hydrogen as energy vectors is just on its start.

Complex metal hydrides of general formula, ABH4 (A = alkali metals, B = third group elements such as B, Al, Ga) are potential candidates as hydrogen storage media for transportation. Thermal decomposition of complex hydrides generates hydrogen at elevated temperatures. The by -products of the dehydrogenation process can be regenerated using gaseous hydrogen at suitable temperature and pressure. The initial steps of thermal decomposition of NaAlH4 may be more complicated from the decomposition pathway reported in the literature. Close examination using thermal analysis by TGA, DSC and XRD measurements over the temperature range 30–500°C showed that the initial evolution of hydrogen occurred at a slow rate at ∼80°C, prior to fast decomposition at 190°C and at 260°C. Four regions of weight loss and five major endothermic peaks were measured during the thermal analysis. The effect of heating rate on the thermal analysis response showed that a high resolution of the thermal processes could be achieved at higher heating rates. Thermodynamic data was obtained for the various steps in the decomposition process including the formation of intermediate phases Na 3AlH6, and NaH. We also found that the decomposition of NaH is highly pressure dependent probably due to the high compressibility of the diffuse H− anion. The crystal-chemistry of NaAlH4 during decomposition has been established using X-ray diffraction analysis.

Gd(1−x)SrxCoO(3−Δ) (GSC) is a promising cathode material system for use in IT-SOFCs due to its high catalytic activity for oxygen reduction and appreciable conductivity. However, it has a high thermal expansion coefficient that is unmatched to the common IT-SOFC electrolyte material, Ce0.8Gd0.2O(2−Δ) (CGO). Gd0.8Sr0.2CoO(3−Δ) (GS20C) was determined to provide the best balance of properties as a base composition in the GSC system for further study. GS20C exhibited electrical conductivity of 400 S cm−1 at 600°C and a linear thermal expansion coefficient of 23 ppm/°C. Manipulation of the Co-site in GS20C by Fe substitution to form Gd(0.8)Sr(0.2)Co(1−y)FeyO(3−Δ) (GS20CFY, Y= 0, 20, 40, 60, 80, 100 atomic%) resulted in a dramatic decrease in the thermal expansion coefficient to a level close to that of the electrolyte (∼13 ppm/°C). However, the decrease in thermal expansion was accompanied by a large decrease in the conductivity as the iron content was increased in the system (to ∼10 S cm−1). Alternatively, formation of GS20C/CGO composite cathodes resulted in thermal matching with the electrolyte material up to the IT-SOFC operating temperature of approximately 600°C with the maintenance of high electrical conductivity. Composite GS20C/CGO cathodes may reduce the problems associated with poor GSC thermal matching to the electrolyte without compromising other important cathodic properties.

A force field methodology has been developed for the description of carbon-carbon and carbon-molecular hydrogen interactions that is ideally suited to modeling hydrogen adsorption on single-walled carbon nanotubes (SWNT). The method makes use of existing parameters of potential functions developed for sp2 and sp3 hybridized carbon atoms and allows accurate representation of molecular forces on curved carbon surfaces. This approach has been used in molecular dynamics (MD) simulations for hydrogen adsorption in SWNT. The results reveal significant nanotube deformations, consistent with ab initio MD simulations, and the calculated energies of adsorption at room temperature are comparable to the reported experimental heats of adsorption for H2 in SWNT. The efficiency of this new method has permitted the MD simulation of hydrogen adsorption on a wide range of SWNT types, varying such parameters as nanotube diameter and chirality. The results show that these SWNT physical parameters have a substantial effect on the energies of adsorption and hydrogen capacities.