Nanoarchitectures Based on Layered Titanosilicates Supported on Glass Fibers: Application to Hydrogen Storage

This work reports on the synthesis of nanosheets of layered titanosilicate JDF-L1 supported on commercial E-type glass fibers with the aim of developing novel nanoarchitectures useful as robust and easy to handle hydrogen adsorbents. The preparation of those materials is carried out by hydrothermal reaction from the corresponding gel precursor in the presence of the glass support. Because of the basic character of the synthesis media, silica from the silicate-based glass fibers can be involved in the reaction, cementing its associated titanosilicate and giving rise to strong linkages on the support with the result of very stable heterostructures. The nanoarchitectures built up by this approach promote the growth and disposition of the titanosilicate nanosheets as a house-of-cards radially distributed around the fiber axis. Such an open arrangement represents suitable geometry for potential uses in adsorption and catalytic applications where the active surface has to be available. The content of the titanosilicate crystalline phase in the system represents about 12 wt %, and this percentage of the adsorbent fraction can achieve, at 298 K and 20 MPa, 0.14 wt % hydrogen adsorption with respect to the total mass of the system. Following postsynthesis treatments, small amounts of Pd (<0.1 wt %) have been incorporated into the resulting nanoarchitectures in order to improve their hydrogen adsorption capacity. In this way, Pd-layered titanosilicate supported on glass fibers has been tested as a hydrogen adsorbent at diverse pressures and temperatures, giving rise to values around 0.46 wt % at 298 K and 20 MPa. A mechanism of hydrogen spillover involving the titanosilicate framework and the Pd nanoparticules has been proposed to explain the high increase in the hydrogen uptake capacity after the incorporation of Pd into the nanoarchitecture.

Microstructure of MmM(5)/Mg multi-layer hydrogen storage films prepared by magnetron sputtering

Multi-layer hydrogen storage thin films with Mg and MmNi(3.5)(CoAlMn)(1.5) (here Mm denotes La-rich mischmetal) as alternative layers were prepared by direct current magnetron sputtering. Transmission electron microscopy investigation shows that the microstructure of the MmNi(3.5)(CoAlMn)(1.5) and Mg layers are significantly different although their deposition conditions are the same. The MmNi(3.5)(CoAlMn)(1.5) layer is composed of two regions: one is an amorphous region approximately 4 nm thick at the bottom of the layer and the other is a nanocrystalline region on top of the amorphous region. The Mg layer is also composed of two regions: one is a randomly orientated nanocrystalline region 50 nm thick at the bottom of the layer and the other is a columnar crystallite region on top of the nanocrystalline region. These Mg columnar crystallites have their [001] directions parallel to the growth direction and the average lateral size of these columnar crystallites is about 100 nm. A growth mechanism of the multi-layer thin films is discussed based on the experiment results. Wiley-Liss, Inc.

Hydrogen storage of magnesium-based nanocomposites system

Hydrogen storage in traditional metallic hydrides can deliver about 1.5 to 2.0 wt pct hydrogen but magnesium hydrides can achieve more than 7 wt pct. However, these systems suffer from high temperature release drawback and chemical instability problems. Recently, big improvements of reducing temperature and increasing kinetics of hydrogenation have been made in nanostructured Mg-based composites. This paper aims to provide an overview of the science and engineering of Mg materials and their nanosized composites with nanostructured carbon for hydrogen storage. The needs in research including preparation of the materials, processing and characterisation and basic mechanisms will be explored. The preliminary experimental results indicated a promising future for chemically stable hydrogen storage using carbon nanotubes modified metal hydrides under lower temperatures.

Hydrogen storage properties of MgH2/SWNT composite prepared by ball milling

A systematic investigation was performed on the hydrogen storage properties of mechano-chemically prepared MgH2/Single-walled carbon nanotube (SWNT) composites. It is found that the hydrogen absorption capacity and hydriding kinetics of the composites were dependent on the addition amount of SWNTs as well as milling time. A 5 wt.% addition of SVVNTs is optimum to facilitate the hydrogen absorption and desorption of MgH2. The composite MgH2/5 wt.% SWNTs milled for 10h can absorb 6.7 wt.% hydrogen within about 2 min at 573 K, and desorb 6 wt.% hydrogen in about 5 min at 623 K. Prolonging the milling time over 10 h leads to a serious degradation on hydrogen storage property of the MgH2/SWNT composite, and property/structure investigations suggest that the property degradation comes from the structure destruction of the SWNTs. (c) 2005 Elsevier B.V. All rights reserved.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/ gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Effect of carbon/noncarbon addition on hydrogen storage behaviors of magnesium hydride

Various Mg/carbon and Mg/noncarbon composite systems were prepared by mechanical milling and their hydrogen storage behaviors were investigated. It was found that all the carbon additives exhibited prominent advantage over the noncarbon additives, such as BN nanotubes (BNNTs) or asbestos in improving the hydrogen capacity and dehydriding/hydriding kinetics of Mg. And among the various carbon additives, purified single-walled carbon nanotubes (SWNTs) exhibited the most prominent catalytic effect on the hydrogen storage properties of Mg. The hydrogen capacities of all Mg/C composites at 573 K reached more than 6.2 wt.% within 10 min, about 1.5 wt.% higher than that of pure MgH2 at the identical operation conditions. Under certain operation temperatures, H-absorption/desorption rates of Mg/carbon systems were over one order of magnitude higher than that of pure Mg. Furthermore, the starting temperature of the desorption reaction of MgH2 has been lowered to 60 K by adding SWNTs. On the basis of the hydrogen storage behavior and structure/phase investigations, the possible mechanism involved in the property improvement of Mg upon adding carbon materials was discussed. (c) 2005 Elsevier B.V. All rights reserved.

Effects of carbon nanotubes and metal catalysts on hydrogen storage in magnesium nanocomposites

This paper reports a study on nanostructured magnesium composites with carbon nanotubes (CNTs) and catalytic transition metals with high H-2 adsorption capacity and fast adsorption kinetics at reduced hydrogenation temperatures. Nanostructures in such a composite are shown to be responsible for improvements in both adsorption capacity and kinetics. It is found that the carbon nanotubes significantly increase the hydrogen storage capacity, and the catalytic transition metals (Fe and Ti) greatly improve the kinetics. This could be understood from the enhancement of diffusion by CNTs and decrease in energy barrier of hydrogen dissociation at the magnesium surface.

Computational study of methyl derivatives of ammonia borane for hydrogen storage

The structures and thermodynamic properties of methyl derivatives of ammonia–borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller–Plesset perturbation theory. It is found that, with respect to pure AB, methyl ammonia–boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

Quest for new materials: Inorganic chemistry plays a crucial role

There is an endless quest for new materials to meet the demands of advancing technology. Thus, we need new magnetic and metallic/semiconducting materials for spintronics, new low-loss dielectrics for telecommunication, new multi-ferroic materials that combine both ferroelectricity and ferromagnetism for memory devices, new piezoelectrics that do not contain lead, new lithium containing solids for application as cathode/anode/electrolyte in lithium batteries, hydrogen storage materials for mobile/transport applications and catalyst materials that can convert, for example, methane to higher hydrocarbons, and the list is endless! Fortunately for us, chemistry - inorganic chemistry in particular - plays a crucial role in this quest. Most of the functional materials mentioned above are inorganic non-molecular solids, while much of the conventional inorganic chemistry deals with isolated molecules or molecular solids. Even so, the basic concepts that we learn in inorganic chemistry, for example, acidity/basicity, oxidation/reduction (potentials), crystal field theory, low spin-high spin/inner sphere-outer sphere complexes, role of d-electrons in transition metal chemistry, electron-transfer reactions, coordination geometries around metal atoms, Jahn-Teller distortion, metal-metal bonds, cation-anion (metal-nonmetal) redox competition in the stabilization of oxidation states - all find crucial application in the design and synthesis of inorganic solids possessing technologically important properties. An attempt has been made here to illustrate the role of inorganic chemistry in this endeavour, drawing examples from the literature its well as from the research work of my group.

Electrochemical investigation of single-walled carbon nanotubes for hydrogen storage

Electrodes made of purified and open single walled carbon nanotubes behave like metal hydride electrodes in Ni-MH batteries, showing high electrochemical reversible charging capacity up to 800 mAh g(-1) corresponding to a hydrogen storage capacity of 2.9 wt% compared to known AB(5), AB(2) metal hydride electrodes. (C) 2000 Elsevier Science Ltd. All rights reserved.

Hydrolysis of Ammonia Borane as a Hydrogen Source: Fundamental Issues and Potential Solutions Towards Implementation

In todays era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO2-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B?N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt?% H2 and 0.145 kg?H?2?L-1, have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications.

Effects of heat exchanger design on the performance of a solid state hydrogen storage device

Heat exchanger design plays a significant role in the performance of solid state hydrogen storage device. In the present study, a cylindrical hydrogen storage device with an embedded annular heat exchanger tube with radial circular copper fins, is considered. A 3-D mathematical model of the storage device is developed to investigate the sorption performance of metal hydride (MH). A prototype of the device is fabricated for 1 kg of MH alloy, LaNi5, and tested at constant supply pressure of hydrogen, validating the simulation results. Absorption characteristics of storage device have been examined by varying different operating parameters such as hydrogen supply pressure and cooling fluid temperature and velocity. Absorption process is completed in 18 min when these parameters are 15 bar, 298 K and 1 m/s respectively. A study of geometric parameters of copper fins (such as perforation, number and thickness of fin) has been carried out to investigate their effects on absorption process. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.