Potential Hydrogen Storage Material Research Articles

Nitrogen Doped Graphene as Potential Material for Hydrogen Storage

The nitrogen doped graphene was synthesized by hydrothermal route utilizing 2-Chloroethylamine hydrochloride as nitrogen precursor in the presence of graphene oxide (GO). Nitrogen-doped graphene material is developed for its application in hydrogen storage at room temperature. Nitrogen doped graphene layered material shows ~1.5 wt% hydrogen storage capacity achieved at room temperature and 90 bar pressure.

A theoretical study of high-pressure-induced phases of LiAlH4 using calculated NQCC parameters

Quadrupolar parameters of nuclei can be used as a tool to understand the electronic structure of compounds. Lithium alanate (LiAlH4) is a potential hydrogen storage material because of its high capacity of 10.5 wt % H2. However, the drawbacks of its dehydrogenation process are the relatively high temperatures and the slow dehydrogenation kinetics; furthermore, its reversibility is rather poor. Understanding the bonding nature of Al and H is essential for improving its dehydrogenation performance. In this work the charge density distribution in LiAlH4 is studied. Thus using calculated nuclear quadrupole coupling constants of hydrogens (2H-NQCCs), the electronic structure of α-LiAlH4 with high pressure forms of LiAlH4, (β- and γ-LiAlH4) were compared. The results show that easier condition for dehydrogenation is expected in β-LiAlH4. Comparison of calculated dehydrogenation enthalpies of LiAlH4 phases verifies this prediction. The electric field gradient (EFG) of quadrupolar nuclei were calculated to obtain NQCC parameters. All calculations performed using Gaussian 03 at B3LYP/6-31G* level of theory.

Ti-decorated B38 fullerene: A high capacity hydrogen storage material

In the present study we investigate the stabilities, electronic properties and the hydrogen storage capacity of Ti-decorated B38 fullerene. All calculations have been performed by using first-principles calculations based on density functional theory. Our results show Ti atoms can be attached on top of the center of hexagonal holes of B38 fullerene with large binding energy (5.67 eV). Each Ti atom can bind up to six hydrogen molecules with an average adsorption energy of 0.22 eV/H2. While the B38 fullerene coated with 4 Ti atoms (4Ti/B38) can store 24 H2 molecules, the gravimetric density reaches up to 7.44 wt% with an average adsorption energy of 0.23 eV/H2. Based on these results we infer that Ti-decorated B38 fullerene is a potential material for hydrogen storage with high capacity and might motivate active experimental efforts in designing hydrogen storage media.

Mechanistic insights of metal acetylacetonate-aided dehydrocoupling of liquid-state ammonia borane NH3BH3

Ammonia borane NH3BH3 solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like Fe(O2C5H7)3, Co(O2C5H7)2, Ni(O2C5H7)2, Pd(O2C5H7)2, Pt(O2C5H7)2 and Ru(O2C5H7)3 are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at 50oC. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the 11B{1H} NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.

Prediction of new stable structure, promising electronic and thermodynamic properties of MoS3: Ab initio calculations

Abstract MoS3 has attracted considerable attention as potential hydrogen storage material due to the interaction between the hydrogen and unsaturated sulfur atoms. However, its structure and physical properties are unknown. By means of first-principles approach and Inorganic crystal structure Database (ISCD), we systematically investigated the structure, relevant physical and thermodynamic properties of MoS3. Phonon dispersion, electronic structure, band structure and heat capacity are calculated in detail. We predicted the orthorhombic B2ab (SrS3-type) and tetragonal P-421m (BaS3-type) structures of MoS3, which prefers to form the SrS3-type (Space group: B2ab, No.41) structure at the ground state. High pressure results in structural transition from SrS3-type structure to BaS3-type structure. This sulfide exhibits a degree of metallic behavior. The calculated heat capacity of MoS3 with SrS3-type structure is about of 39 J/(mol·K).

High-capacity hydrogen storage in Li-adsorbed g-C3N4

Since hydrogen is a kind of potential source of efficient and pollution-free energy, it has attracted great research interests in recent years. However, the lack of safe and efficient hydrogen storage materials has blocked the rapid development of hydrogen energy. Here, we explored the possibility of Li-decorated g-C3N4 as a kind of potential hydrogen storage materials based on first-principles calculations. Our results demonstrated that the adsorption energy of Li atoms on g-C3N4 is much larger than the cohesive energy of bulk Li. Importantly, we find that the binding energy of each H2 molecule is about 0.29 eV, which is quite suitable for hydrogen storage. Furthermore, the estimated hydrogen storage capacity is around 9.2 wt %, which beyonds the goal of DOE. Thus, we predicted that Li-decorated g-C3N4 may act as the potential hydrogen storage materials.

In Pursuit of Sustainable Hydrogen Storage with Boron-Nitride Fullerene as the Storage Medium.

Using well calibrated DFT studies we predict that experimentally synthesized B24 N24 fullerene can serve as a potential reversible chemical hydrogen storage material with hydrogen-gas storage capacity up to 5.13 wt %. Our theoretical studies show that hydrogenation and dehydrogenation of the fullerene framework can be achieved at reasonable rates using existing metal-free hydrogenating agents and base metal-containing dehydrogenation catalysts.

A theoretical study of the spectroscopic properties of B2H6 and of a series of Bx[formula omitted] species (x = 1−12, y = 3−14, z = 0−2): From BH3 to B12[formula omitted

The characterization of boron-hydrogen compounds is an active research area which encompasses subjects as diverse as the chemistry and structures of closoboranes or the thermal decomposition mechanism of the borohydrides. Due to their high gravimetric hydrogen content, borohydrides are considered as potential hydrogen storage materials. Their thermal decompositions are multistep processes, for which the intermediate products are not easily identified. To help address this issue, we have extensively investigated the vibrational and NMR properties of 21 relevant BmHnz− boron-hydrogen species (m = 1–12; n = 1–14; z = 0–2) within density functional theory. We could thus show that the B3LYP-D2 dispersion-corrected hybrid can be used in combination with the large cc-pVTZ basis set for the reliable prediction of the 11B and 1H NMR spectra of the boron-hydrogen species, and also for the reliable prediction of their IR and Raman spectra while taking into account the anharmonicity of their molecular vibrations.

An improved synthesis of unsolvated NaB3H8 and its application in preparing Na2B12H12

Octahydrotriborates are potential hydrogen storage materials and chemical vapor deposition precursors to boride films. Their syntheses have been quite challenging, however. In this paper, an improved facile route for the preparation of unsolvated sodium octahydrotriborate (NaB3H8), which is an important precursor to other octahydrotriborates and derivatives, is reported. The key steps in the synthesis involve dispersing Na finely in inert media and preparing fresh tetrahydrofuran (THF)·BH3 at room temperature. High purity unsolvated NaB3H8 can be obtained in tens of grams or more in one batch, depending on the reactor size. Using NaB3H8 as the precursor, sodium dodecaborate (Na2B12H12) has been successfully synthesized. Both octahydrotriborates and dodecaborates have been observed as intermediates during the thermal dehydrogenation of borohydrides, and their facile syntheses would facilitate mechanistic studies on the hydrogen storage of borohydrides, among other potential applications.

External electric field: An effective way to prevent aggregation of Mg atoms on γ-graphyne for high hydrogen storage capacity

In this article, we investigate the hydrogen storage capacity of Mg-decorated γ-graphyne (Mg-G) based on DFT calculations. Our results indicate that an external electric field can effectively prevent Mg atoms aggregating on γ-graphyne sheet. The Mg-G, after electric field (F=0.05V/nm) treatment, can store up to ten H2 molecules and the hydrogen storage capacity is 10.64wt%, with the average adsorption energy of 0.28eV/H2. Our calculations demonstrate that Mg-G is a potential material for hydrogen storage with high capacity and might motivate active experimental efforts in designing hydrogen storage media.

Few-layer graphene-like flakes derived by plasma treatment: A potential material for hydrogen adsorption and storage

A novel, one-step, wet-free, environmental friendly and high-yield method for producing few-layer graphene powders with large surface areas (up to 800 m2/g) and narrow nanopore sizes (0.7–0.8 nm) using plasma-induced exfoliation of natural graphite is presented. Advanced characterization techniques were employed, including scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and N2 gas adsorption/desorption measurements at 77 K, to investigate the morphological, elemental, structural and textural/porosity properties of these nanomaterials. Fully reversible H2 gas adsorption/desorption isotherms with maximum gravimetric capacities of up to ∼2 wt.% at 77 K and ∼60 bar are reported here. The H2 storage performance at 77 K is well correlated with certain textural features such as specific surface area and microporosity. The results of this work provide a valuable feedback for further research on plasma-processed graphene-based materials towards efficient H2 storage via cryo-adsorption.

Effect of Magnesium Fluoride on Hydrogenation Properties of Magnesium Hydride

A cost effective catalyst is of great importance for consideration of MgH2 as potential hydrogen storage material. In this regard, we investigated the catalytic role of alkaline metal fluoride on the hydrogen storage behavior of MgH2. Samples were synthesized by admixing 5 mol % MgF2 into MgH2 powder using planetary ball mill. Hydrogenation measurements made at 335 °C showed that in comparison to only 70% absorption by pure MgH2, catalyzed material absorbed 92% of theoretical capacity in less than 20 min and desorbed completely in almost the same time. Sorption studies done at lower temperatures revealed that complete absorption at temperature as low as 145 °C is possible. This is due to uniform distribution of MgF2 nano particles within the MgH2 powder. X-ray diffraction patterns also showed the presence of stable MgF2 phase that does not decompose upon hydrogen absorption-desorption. Cyclic measurements done at 310 °C showed negligible loss in the overall storage capacity with cycling. These results reveal that the presence of the chemically inert and stable MgF2 phase is responsible for good reversible characteristic and improved kinetics.

Effect of nickel on hydrogen storage behaviors of carbon aerogel hybrid

Limited conventional energy resources and serious environmental calamities have motivated researchers to find new and efficient sources of energy. The considerable efforts devoted to this end include the development of bio-diesel, solar cells, coal liq-uefaction/gasification technologies, and fuel cells. Hydrogen is considered by many an ideal energy source owing to its renewable and clean energy characteristics. In addition, it mostly produces water, which is eco-friendly compared to the byproducts of many other energy sources [1-6]. To use hydrogen as an energy source, various hydrogen stor -age methods such as the use of metal hydrides, liquefied hydrogen, and adsorption of hydrogen in porous materials have been studied [7-14]. The adsorption of hydrogen in porous materials is particularly suitable for hydrogen storage, which is critical for suit -ably utilizing hydrogen energy, owing to the reversibility and stability of this method. To date, the wide ranging attempts to develop hydrogen storage mechanisms include studies on carbon materials [15-17], metal-organic frameworks, and zeolites [18-21]. Carbon materials offer many advantages for hydrogen storage, such as easy preparation, suitable surface functional groups, low mass density, thermal stability, and hydropho -bicity [22-24]. Carbon aerogels (CAs) in particular have been recognized as potential hydrogen storage materials because of their suitable structural properties, controllable mass densities, high specific surface areas, and mesopore volumes. However, it is neces -sary to modify the surfaces of carbon materials in order to reach the hydrogen storage capacities determined by the US Department of Energy (DOE).Carbon materials containing transition metals such as platinum, copper, vanadium, and nickel exhibit attractive hydrogen storage properties [10,22,25]. Nickel is particularly prom -ising since it is easily obtained on Earth, and it is inexpensive compared to other metals and enhances hydrogen storage properties. Improved hydrogen storage capacities have been obtained with nickel-plated porous carbon nanofibers owing to the spillover of hydrogen molecules onto the metal-carbon interfaces. In general, the presence of nickel particles on carbon materials has been shown to enhance the hydrogen storage capacity [3,9,19].In this work, CAs were chemically activated by KOH to produce well-developed pore structures and ultimately increase the hydrogen storage capacities. Nickel-loaded activated carbon aerogels (ACAs/Ni hybrid materials) with various nickel content were prepared. Ni particles were loaded onto ACAs to introduce hydrogen-favorable active sites onto the ACA surfaces and improve the hydrogen storage capacities.The CAs were prepared using resorcinol as the carbon precursor and formaldehyde as the initiator. Resorcinol (7.5 g) was dissolved in a solution of distilled water (75 mL) and formaldehyde (25 g). Sodium carbonate was then added to this solution, and the mixture was stirred for 3 h in an open container and dried for 3 h at room temperature. Subsequently, the wet gel was dried at 80°C for 48 h and then immersed in an acetone solution for 24 h without stirring. The aerogels were obtained after drying at 80°C for 24 h. Prior to use, the aerogels were carbonized in a furnace with a heating rate of 2°Cmin

Quantitative Spectra–Structure Relations for Borohydrides

Among the different potential hydrogen storage materials, borohydrides have been largely investigated because of their high gravimetric and volumetric hydrogen content. In the analysis of borohydrides, vibrational spectroscopy plays an important role since it gives information on the local structure of the BH4– ion inside the solid. Here the GF method, developed by Wilson, is used in order to determine the local symmetry of BH4– in solid borohydrides starting from their vibrational spectra. Two different cases of deformations of BH4– are considered. In the first case, the effects of small angular variations on the vibrational spectra of borohydrides will be taken into account; starting from the splitting of the bands corresponding to the deformation modes, the angular deformations will be estimated. In the second one, the BH4– under chemical pressure (in different cubic alkali halides) is considered; in this case, the symmetry of the BH4– remains Td, while the bond lengths change according to the pressure...

New Insights into the Thermodynamic Behavior of 2LiBH4–MgH2 Composite for Hydrogen Storage

The composite 2LiBH4:MgH2 has been studied as a potential hydrogen storage material due to its high storage capacity. The present work is aimed at clarifying the thermodynamic behavior of the system, especially within the temperature region above 400 °C. Different reaction paths which have important implication for storage applications during hydrogen absorption and desorption at various temperatures were revealed. At temperatures over 413 °C, two different absorption pressure plateaus are observed. This indicates that two different reactions occur: Mg hydrogenation at higher pressures and the re-formation of LiBH4 from H2, LiH, and MgB2 at lower pressures. On the other hand, at temperatures below 413 °C only one plateau is present in the system. During desorption, the double plateau can be observed at temperatures as low as 375 °C. This effect restricts the applicability of this composite as a hydrogen storage material.

Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System.

Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH2)2) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH2)2 lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH2)2 system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H2 at 150 °C.

Transition metal Ti coated porous fullerene C24B24: Potential material for hydrogen storage

The hydrogen storage capacity of transition metal Ti atoms decorated porous fullerene C24B24 is investigated by the pseudopotential density functional method. The C24B24 cage contains six B4 rings with the average diameter of 3.88 Å. The Ti atoms are strongly bound to six B4 rings. Each Ti atom can adsorb up to six H2 molecules. The calculated average adsorption energies per H2 for (Ti-nH2)6C24B24(n = 1–6) are in the energy range from 0.24 to 0.55 eV, which is suitable for hydrogen storage at near-ambient conditions. The Dewar–Kubas interaction dominates the adsorption of H2 on the outer surface of Ti6C24B24. The largest hydrogen gravimetric density of (Ti–6H2)6C24B24 is 8.1 wt%, exceeding the 5.5 wt% by the year 2017 specified by the US department of energy (DOE). Therefore, the stable Ti6C24B24 can be applied as one candidate for hydrogen storage materials at near-ambient conditions.

Key study on the potential of hydrazine bisborane for solid- and liquid-state chemical hydrogen storage.

Hydrazine bisborane N2H4(BH3)2 (HBB; 16.8 wt %) recently re-emerged as a potential hydrogen storage material. However, such potential is controversial: HBB was seen as a hazardous compound up to 2010, but now it would be suitable for hydrogen storage. In this context, we focused on fundamentals of HBB because they are missing in the literature and should help to shed light on its effective potential while taking into consideration any risk. Experimental/computational methods were used to get a complete characterization data sheet, including, e.g., XRD, NMR, FTIR, Raman, TGA, and DSC. From the reported results and discussion, it is concluded that HBB has potential in the field of chemical hydrogen storage given that both thermolytic and hydrolytic dehydrogenations were analyzed. In solid-state chemical hydrogen storage, it cannot be used in the pristine state (risk of explosion during dehydrogenation) but can be used for the synthesis of derivatives with improved dehydrogenation properties. In liquid-state chemical hydrogen storage, it can be studied for room-temperature dehydrogenation, but this requires the development of an active and selective metal-based catalyst. HBB is a thus a candidate for chemical hydrogen storage.

Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

Hydrazine borane N2H4BH3 and alkali derivatives (i.e., lithium, sodium and potassium hydrazinidoboranes MN2H3BH3 with M = Li, Na and K) have been considered as potential chemical hydrogen storage materials. They belong to the family of boron- and nitrogen-based materials and the present article aims at providing a timely review while focusing on fundamentals so that their effective potential in the field could be appreciated. It stands out that, on the one hand, hydrazine borane, in aqueous solution, would be suitable for full dehydrogenation in hydrolytic conditions; the most attractive feature is the possibility to dehydrogenate, in addition to the BH3 group, the N2H4 moiety in the presence of an active and selective metal-based catalyst but for which further improvements are still necessary. However, the thermolytic dehydrogenation of hydrazine borane should be avoided because of the evolution of significant amounts of hydrazine and the formation of a shock-sensitive solid residue upon heating at >300 °C. On the other hand, the alkali hydrazinidoboranes, obtained by reaction of hydrazine borane with alkali hydrides, would be more suitable to thermolytic dehydrogenation, with improved properties in comparison to the parent borane. All of these aspects are surveyed herein and put into perspective.

Urea and deuterium mixtures at high pressures.

Urea, like many network forming compounds, has long been known to form inclusion (guest-host) compounds. Unlike other network formers like water, urea is not known to form such inclusion compounds with simple molecules like hydrogen. Such compounds if they existed would be of interest both for the fundamental insight they provide into molecular bonding and as potential gas storage systems. Urea has been proposed as a potential hydrogen storage material [T. A. Strobel et al., Chem. Phys. Lett. 478, 97 (2009)]. Here, we report the results of high-pressure neutron diffraction studies of urea and D2 mixtures that indicate no inclusion compound forms up to 3.7 GPa.