First-principles study of LiBH4 nanoclusters interaction with models of porous carbon and silica scaffolds

Density functional theory calculations of an interaction of LiBH₄ represented by n = 2−6 and 12 formula units nanoclusters with models of activated carbon and porous silica show that on both non-defective substrates only physisorption is observed for all cluster sizes. The binding energies are low, reaching up to −43 kJ/mol for smallest clusters. The charge transfer between LiBH₄ and the support is not observed. On defective graphene (LiBH₄)₂ may adsorbed dissociatively. Hydrogens detached from BH₄ groups saturates under-coordinated C atoms while the binding between BH₃ moiety and underlying C atoms restores sp³-hybridization in the BH₄ group. The dissociative adsorption of LiBH₄ clusters leads to the retrieval of the three-fold coordination of the C atoms, the subsequent (LiBH₄)₂ physisorps with the differential heat of adsorption not exceeding −46 kJ/mol. The present calculations indicate that chemical interaction between matrix and lithium borohydride, leading to a destabilization of LiBH₄, takes place until substrate's defects remain unsaturated.     

LiBH4·NH3BH3: A new lithium borohydride ammonia borane compound with a novel structure and favorable hydrogen storage properties

Mechanically milling ammonia borane and lithium borohydride in equivalent molar ratio results in the formation of a new complex, LiBH₄·NH₃BH₃. Its structure was successfully determined using combined X-ray diffraction and first-principles calculations. LiBH₄·NH₃BH₃ was carefully studied in terms of its decomposition behavior and reversible dehydrogenation property, particularly in comparison with the component phases. In parallel to the property examination, X-ray diffraction and Fourier transformation infrared spectroscopy techniques were employed to monitor the phase evolution and bonding structure changes in the reaction process. Our study found that LiBH₄·NH₃BH₃ first disproportionates into (LiBH₄)₂·NH₃BH₃ and NH₃BH₃, and the resulting mixture exhibits a three-step decomposition behavior upon heating to 450 °C, totally yielding ∼15.7 wt% hydrogen. Interestingly, it was found that h-BN was formed at such a moderate temperature. And owing to the in situ formation of h-BN, LiBH₄·NH₃BH₃ exhibits significantly improved reversible dehydrogenation properties in comparison with the LiBH₄ phase.     

Mechano-chemical synthesis of manganese borohydride (Mn(BH4)2) and inverse cubic spinel (Li2MnCl4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior

Manganese borohydride (Mn(BH₄)₂) was successfully synthesized by a mechano-chemical activation synthesis (MCAS) from lithium borohydride (LiBH₄) and manganese chloride (MnCl₂) by applying high energy ball milling for 30 min. For the first time a wide range of molar ratios n = 1, 2, 3, 5, 9 and 23 in the (nLiBH₄ + MnCl₂) mixture was investigated. During ball milling for 30 min the mixtures release only a very small quantity of H₂ that increases with the molar ratio n but does not exceed ∼0.2 wt.% for n = 23. However, longer milling duration leads to more H₂ released. For the equimolar ratio n = 1 the principal phases synthesized are Li₂MnCl₄, an inverse cubic spinel phase, and the Mn(BH₄)₂ borohydride. For n = 2 a LiCl salt is formed which coexists with Mn(BH₄)₂. With the n increasing from 3 to 23 LiBH₄ is not completely reacted and its increasing amount is retained in the microstructure coexisting with LiCl and Mn(BH₄)₂. Gas mass spectrometry during Temperature Programmed Desorption (TPD) up to 450 °C shows the release of hydrogen as a principal gas with a maximum intensity around 130–150 °C accompanied by a miniscule quantity of borane B₂H₆. The intensity of the B₂H₆ peak is 200–600 times smaller than the intensity of the corresponding H₂ peak. In situ heating experiments using a continuous monitoring during heating show no evidence of melting of Mn(BH₄)₂ up to about 270–280 °C. At 100 °C under 1 bar H₂ pressure the ball milled n = 2 and 3 mixtures are capable of desorbing quite rapidly ∼4 wt.% H₂ which is a very large amount of H₂ considering that the mixture also contains 2 mol of LiCl salt. The H₂ quantities experimentally desorbed at 100 and 200 °C do not exceed the maximum theoretical quantities of H₂ expected to be desorbed from Mn(BH₄)₂ for various molar ratios n. It clearly confirms that the contribution from B₂H₆ evolved is negligibly small (if any) when desorption occurs isothermally in the practical temperature range 100–200 °C. It is found that the ball milled mixture with the molar ratio n = 3 exhibits the highest rate constant k and the lowest apparent activation energy for dehydrogenation, E_A ∼ 102 kJ/mol. Decreasing or increasing the molar ratio n below or above 3 increases the apparent activation energy. Ball milled mixtures with the molar ratio n = 2 and 3 discharge slowly H₂ during storage at room temperature and 40 °C. The addition of 5 wt.% nano-Ni with a specific surface area of 60.5 m²/g substantially enhances the rate of discharge at 40 °C.     

Hydrogen generation from noncatalytic hydrolysis of LiBH4/NH3BH3 mixture for fuel cell applications

Ammonia borane (NH₃BH₃) and lithium borohydride (LiBH₄) are promising hydrides as they contain 19.6 wt.% and 18.5 wt.% hydrogen respectively. However, hydrolysis of NH₃BH₃ needs catalysts or high temperature to initiate the release of hydrogen. On the other hand, hydrolysis of LiBH₄ is incomplete, because the agglomeration of LiBH₄ and its products limits its full utilization. In the present work, hydrolysis performance of LiBH₄/NH₃BH₃ mixture was investigated. The results show that LiBH₄/NH₃BH₃ mixture can fully release its theoretical amount of hydrogen at room temperature without catalysts. In the presence of LiBH₄, NH₃BH₃ can be fully hydrolyzed at room temperature. In return, in the presence of NH₃BH₃, the agglomeration can be avoided resulting in a complete hydrolysis process. Our results indicate that the improvements are attributed to the intermolecular electron migration between LiBH₄ and NH₃BH₃, which changes the reactivity of these compounds. Hydrolytic heat of LiBH₄ also contributes to the promoted hydrolysis of NH₃BH₃. Our results present a novel strategy for noncatalytic hydrolysis of NH₃BH₃ and LiBH₄ for proton exchange membrane fuel cell applications.     

Li2(NH2BH3)(BH4)/LiNH2BH3: The first metal amidoborane borohydride complex with inseparable amidoborane precursor for hydrogen storage

A novel lithium amidoborane borohydride complex, Li₂(NH₂BH₃)(BH₄), was synthesized using mechanochemical method and its crystal structure was successfully determined by a combination of X-ray diffraction (XRD) analysis and first-principles calculations. Interestingly, this compound does not exist as a pure phase, but requires almost equivalent amount of amorphous LiAB as a stabilizing agent. In this paper, we report a careful study of the structure, property, and dehydrogenation mechanism of the 1:1 Li₂(NH₂BH₃)(BH₄)/LiAB composite. This composite can release ∼8 wt% H₂ at 100 °C via a two-step dehydrogenation process, with dehydrogenation kinetics better than the parenting phases. The composite and its dehydrogenation products were characterized by the combined XRD, Fourier transformation infrared (FTIR) spectroscopy, and solid-state ¹¹B MAS NMR techniques. Selective deuterium labeling was performed to elucidate a reaction sequence for the hydrogen release by analyzing the released gases.     

Superior low-temperature hydrogen release from the ball-milled NH3BH3–LiNH2–LiBH4 composite

In the present study, we employed a multi-component combination strategy to constitute an AB/LiNH₂/LiBH₄ composite system. Our study found that mechanically milling the AB/LiNH₂/LiBH₄ mixture in a 1:1:1 molar ratio resulted in the formation of LiNH₂BH₃ (LiAB) and new crystalline phase(s). A spectral study of the post-milled and the relevant samples suggests that the new phase(s) is likely ammoniate(s) with a formula of Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄) (0 < x < 1). The decomposition behaviors of the Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄)/xLiAB composite were examined using thermal analysis and volumetric method in a wide temperature range. It was found that the composite exhibited advantageous dehydrogenation properties over LiAB and LiAB·NH₃ at moderate temperatures. For example, it can release ∼7.1 wt% H₂ of purity at temperature as low as 60 °C, with both the dehydrogenation rate and extent far exceeding that of LiAB and LiAB·NH₃. A selectively deuterated composite sample has been prepared and examined to gain insight into the dehydrogenation mechanism of the Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄)/xLiAB composite. It was found that the LiBH₄ component does not participate in the dehydrogenation reaction at moderate temperatures, but plays a key role in strengthening the coordination of NH₃. This is believed to be a major mechanistic reason for the favorable dehydrogenation property of the composite at moderate temperatures.     

Promoted hydrogen release from 3LiBH4/MnF2 composite by doping LiNH2: Elimination of diborane release and reduction of decomposition temperature

The evolution of diborane accompanying H₂ release during the decomposition of transition metal borohydrides reduces the purity of evolved hydrogen and results in capacity loss during cycling. To solve the problem, a small amount of LiNH₂ is doped into a 3LiBH₄/MnF₂ composite and the decomposition properties are investigated. The results show that after doping LiNH₂, the formation of diborane during decomposition is effectively suppressed meanwhile the decomposition temperature is significantly reduced. Around 5 wt.% pure hydrogen can be released at 95–140 °C from 5 wt.% LiNH₂-doped 3LiBH₄/MnF₂ composite. These improvements in the decomposition performance are mainly attributed to the prevention of the formation of B–H–B bonds for B₂H₆ and the destabilization of B–H bonds in borohydrides by the interaction of BH₄⁻ and NH₂⁻.     

Transition metal-catalyzed dehydrogenation of hydrazine borane N2H4BH3via the hydrolysis of BH3 and the decomposition of N2H4

Hydrazine borane N₂H₄BH₃ (denoted HB) is a novel candidate in hydrogen generation by catalytic hydrolysis. The challenge with this material is the dehydrogenation of the N₂H₄ moiety, which occurs after the hydrolysis of the BH₃ group. This challenge requires the utilization of a reactive and selective metal-based catalyst. In this work, we considered various transition metal salts as precursors of in situ forming catalysts by reduction in the presence of HB. According to their reactivity, the metals studied can be classified into 3 groups: (1) Fe- and Re-based catalysts, showing a limited reactivity in the hydrolysis of the BH₃ group; (2) Co-, Ni-, Cu-, Pd-, Pt- and Au-based catalysts, only active in the hydrolysis of BH₃ (3 mol H₂ per mol HB generated); (3) Ru-, Rh, and Ir-based catalysts, being also active in the decomposition of N₂H₄. With the Rh-based catalyst, characterized as agglomerated Rh⁰ nanorods (10 × 4 nm) by XRD, TEM, SAED and XPS, 4.1 mol H₂ + N₂ per mol HB can be produced at 50 °C. Rhodium is thus a possible candidate for synthesizing nanosized particles and bimetallic nanoalloys in order to tune its reactivity and increase its selectivity up to the targeted conversion of 100%. Our main results are reported herein and the behavior of the metals is discussed.     

Enhanced dehydrogenation and rehydrogenation properties of LiBH4 catalyzed by graphene

The investigation of thermally induced dehydrogenation of LiBH₄ reveals that LiBH₄ doped with the graphene catalysts shows superior dehydrogenation and rehydrogenation performance to that of Vulcan XC-72, carbon nanotube and BP2000 doped LiBH₄. For doping with 20 wt.% graphene, thermal dehydrogenation of LiBH₄ is found to start at ca. 230 °C and a total weight loss of 11.4 wt.% can be obtained below 700 °C. With increased loading of graphene within a LiBH₄ sample, the onset dehydrogenation temperature and the two main desorption peaks from LiBH₄ are found to decrease while the hydrogen release amount is found to increase. Moreover, variation of the equilibrium pressure obtained from isotherms measured at 350–450 °C indicate the dehydrogenation enthalpy is reduced from 74 kJ mol⁻¹ H₂ for pure LiBH₄ to ca. 40 kJ mol⁻¹ H₂ for 20 wt.% graphene doped LiBH₄. Importantly, the reversible dehydrogenation/rehydrogenation process was achieved under 3 MPa H₂ at 400 °C for 10 h, with a capacity of ca. 4.0 wt.% in the tenth cycle. Especially, LiBH₄ is reformed and new species, Li₂B₁₀H₁₀, is detected after the rehydrogenation process.     

Cesium hydrazinidoborane,the last of the alkali hydrazinidoboranes,studied as potential hydrogen storage material

Alkali hydrazinidoboranes MN₂H₃BH₃ (M = Li, Na, K, Rb) have been developed for hydrogen storage. To complete the family of MN₂H₃BH₃, we focused on cesium hydrazinidoborane CsN₂H₃BH₃ (CsHB). It has been synthesized by reaction of cesium with hydrazine borane (N₂H₄BH₃) at −20 °C under inert atmosphere, and it has been characterized. A crystalline solid (monoclinic, s.g. P2₁ (No. 4)) has been obtained. Its potential for hydrogen storage has been studied by combining different techniques. It was found that, under heating at constant heating rate (5 °C min⁻¹) or at constant temperature (e.g. 120 °C), CsHB decomposes rather than it dehydrogenates. It releases several unwanted gaseous products (e.g. NH₃, B₂H₆) together with H₂, and transforms into a residue that poses safety issues because of shock-sensitivity and reactivity towards O₂/H₂O. Though the destabilization brought by Cs⁺ onto the anion [N₂H₃BH₃]⁻ has been confirmed, the effect is not efficient enough to avoid the aforementioned drawbacks. All of our results are presented herein and discussed within the context of solid-state hydrogen storage.     

Nanoconfinement of LiBH4·NH3 towards enhanced hydrogen generation

Successful synthesis of LiBH₄·NH₃ confined in nanoporous silicon dioxide (LiBH₄·NH₃@SiO₂) was achieved via a new “ammonia-deliquescence” method, which avoids the involvement of any solvents during the process of synthesis. Compared to the pure LiBH₄·NH₃, the confined LiBH₄·NH₃@SiO₂ exhibited significantly improved dehydrogenation properties, which not only suppressed the emission of NH₃, but also decreased the onset dehydrogenation temperature to 60 °C, thus leading to an enhanced conversion of NH₃ to H₂. In the temperature range of 60–300 °C, the mole ratio of H₂ release for the confined LiBH₄·NH₃@SiO₂ is 85 mol % of the total gas evolved, compared to 2.66 mol % for the pristine LiBH₄·NH₃. Isothermal dehydrogenation results showed that the LiBH₄·NH₃@SiO₂ is able to release about 1.26, 2.09, and 2.35 equiv. of hydrogen, at 150 °C, 200 °C, and 250 °C, respectively. From analysis of the Fourier transform infrared, Raman, and nuclear magnetic resonance spectra of the confined LiBH₄·NH₃@SiO₂ sample heated to various temperatures, as well as its dehydrogenation product under NH₃ atmosphere, it is proposed that the improved dehydrogenation of LiBH₄·NH₃@SiO₂ is mainly attributable to two crucial factors resulting from the nanoconfinement: (1) stabilization of the NH₃ in the nanopores of SiO₂, and (2) enhanced combination of LiBH₄ and NH₃ groups, leading to fast dehydrogenation at low temperature.     

Magnesium borohydride hydrolysis with kinetics controlled by ammoniate formation

The possibility of hydrogen generation by hydrolysis of magnesium borohydride and its ammoniates was explored. Results show that catalyst-free Mg(BH₄)₂ can generate 1700 mL (H₂)·g⁻¹ in 1 min, 2760 mL (H₂)·g⁻¹ in 2 h, and 3004 mL (H₂)·g⁻¹ in 5 h without any diborane (B₂H₆) emission. Mg(BH₄)₂ presents the highest hydrogen yield reported to date. However, the hydrogen generation rate of Mg(BH₄)₂ may be too fast to be controllable in some hydrogen production cases. Therefore, NH₃ was added to form ammoniates to further regulate the hydrogen supply kinetics of Mg(BH₄)₂. The hydrogen yields of Mg(BH₄)₂·0.5NH₃, Mg(BH₄)₂·NH₃, Mg(BH₄)₂·2NH₃, Mg(BH₄)₂·3NH₃ and Mg(BH₄)₂·6NH₃ are 2376, 2029, 1780, 1665 and 1180 mL (H₂) g⁻¹, respectively, which demonstrates a well-controlled hydrogen supply rate. These results indicate that catalyst-free Mg(BH₄)₂ and its ammoniates have good hydrolysis performance and show promise as convenient high-density hydrogen generation materials.     

Effect of the presence of chlorides on the synthesis and decomposition of Ca(BH4)2

Calcium borohydride is one of the most interesting compounds for solid-state hydrogen storage, in particular because of its high hydrogen capacity. In this paper, the synthesis of Ca(BH₄)₂ by metathesis reaction via ball milling of a mixture of LiBH₄ and CaCl₂ is described. The effectiveness of this synthesis technique and the possible substitution of Cl ions in the borohydride phases is analysed depending on the back-pressure used for milling. When performed by ball milling under Ar, the metathesis reaction is not successful. A large quantity of a solid solution Li(BH₄)_1−xCl_x remains in the sample and CaHCl is formed rather than Ca(BH₄)₂. In contrast, the use of H₂ back-pressure during milling favours the borohydride phases rather than CaHCl and leads to the formation of a solid solution Ca(BH₄)_2-yCl_y where [BH₄]⁻ groups are partially substituted by Cl ions. This compound has a similar structure as β-Ca(BH₄)₂ but with smaller lattice parameters. It is present in the as-milled sample together with LiCl and Li(BH₄)_1−xCl_x. The decomposition of the mixture occurs at lower temperature than for pure LiBH₄ but higher than for pure Ca(BH₄)₂. The presence of chlorides in the structure of borohydride compounds changes dramatically the thermal properties of the material prepared and should be considered each time a metathesis reaction is used for synthesis.     

Aqueous hydrazine borane N2H4BH3 and nickel-based catalyst: An effective couple for the release of hydrogen in near-ambient conditions

Nickel-based bimetallic catalysts were screened using the sodium borohydride NaBH₄ hydrolysis and the aqueous hydrazine borane N₂H₄BH₃ dehydrogenation. A total of 22 bimetallic catalysts were synthesized according to an easy process while focusing on metals like Fe, Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt and Au. In the end, the bimetallic candidate Ni_87.5Pt_12.5 showed to be the most active and the most selective for the dehydrogenation of N₂H₄BH₃. At 70?°C, it is able to decompose N₂H₄BH₃ into 5.8 equivalents of H₂+N₂ in less than 12?min such as: N₂H₄BH₃?+?3H₂O?→?0.95 N₂?+?0.1 NH₃?+?B(OH)₃?+?4.85H₂. Durability and stability tests were also performed. In our conditions, Ni_87.5Pt_12.5 was found to suffer from small loss of performance because of an electronic evolution of the catalytic surface leading to modified sorption properties of the catalytic sites. Our main results are reported and discussed herein.     

Enhanced hydrogen reversibility of nanoconfined LiBH4–Mg(BH4)2

This study shows the hydrogen desorption kinetics and reversible hydrogen storage properties of 0.55LiBH₄–0.45Mg(BH₄)₂ melt-infiltrated in different nanoporous carbon aerogels with different BET surface areas of 689 or 2660 m²/g and pore volumes of 1.21 or 3.13 mL/g. These investigations clearly show a significantly improved hydrogen storage capacity after four cycles of hydrogen release and uptake for bulk 0.55LiBH₄–0.45Mg(BH₄)₂ and infiltrated in carbon aerogel and the high surface area scaffold, where 22, 36 and 58% of the initial hydrogen content remain after four cycles of hydrogen release and uptake, respectively. Nanoconfinement in high surface area carbon aerogel appears to facilitate hydrogen release illustrated by release of 13.3 wt% H₂ (93%) and only 8.4 wt% H₂ (58%) from bulk hydride in the first cycle using the same physical condition. Notably, nanoconfinement also appear to have a beneficial effect on hydrogen uptake, since 8.3 wt% H₂ (58%) is released from the high surface area scaffold and only 3.1 wt% H₂ (22%) from the bulk sample during the fourth hydrogen release.     

Synthesis and hydrogen storage properties of lithium borohydride amidoborane complex

A series of mixtures of LiAB/LiBH₄ with different molar ratios were prepared and their hydrogen storage properties were investigated in this study. Among them, a new structure was found in the LiAB/LiBH₄ sample with a molar ratio of 1/1. It is of orthorhombic structure and composed of alternative layers of LiAB and LiBH₄. It shows similar hydrogen desorption behaviors of LiAB–LiBH₄ and LiAB–0.5LiBH₄. For use in hydrogen storage, high hydrogen capacity and low operation temperature are demanded, thus, the dehydrogenation properties of LiAB–0.5LiBH₄ were subsequently measured. Three steps of desorption were observed during the heating process, with a total release of 11.5 wt% H₂ at 500 °C. The reaction path was identified using a combined investigation of XRD and ¹¹B solid state NMR. Dehydrogenation kinetic analyses show that the complex has lower activation energy (61 ± 4 kJ mol⁻¹ H₂) than that of LiAB (71 ± 5 kJ mol⁻¹ H₂). It is likely that dehydrogenation process was promoted due to the presence of LiBH₄.     

Hydrogen production from sodium borohydride originated compounds: Fabrication of electrospun nano-crystalline Co3O4 catalyst and its activity

Electrospun nanofibers are prepared through electrospinning followed by post-treatment and preferred to use in catalytic applications. The electrospinning provides advantages for active catalysts design based on activity profiles and features of catalyst. In the present study, we fabricated nano-crystalline cobalt oxide (Co₃O₄) catalyst by electrospinning technique followed by thermal conditioning. Polyacrylonitrile (PAN) based Co as-spun mats (Co/NMs) with homogeneous diameter were prepared by electrospinnig process under several conditions as applied voltage (15–25 kV), working distance (5–7.5 cm) with the feed rate of 1 ml min⁻¹. The calcination process as a post-treatment was applied at different temperatures (232 °C, 289 °C and 450 °C) to obtain electrospun nano-crystalline Co₃O₄ catalyst. Co/NMs catalysts were characterized by XRD, SEM, TEM, XPS, FT-IR, TG/DTG, and ICP-MS techniques. The parametrically study was performed for evaluating the hydrogen production activity of catalyst from sodium borohydride (NaBH₄, SBH) and its originated compounds as ammonia borane (NH₃BH₃, AB) and methyl-amine borane (CH₃NH₂BH₃, MeAB). The relation between the internal-external properties and catalytic activities of catalysts for hydrogen production was investigated. The beadless Co/NMs-1 catalyst with homogeneous diameter was obtained under electrospinnig process conditions at 15 kV applied voltage and 7.5 cm working distance. All catalysts showed activity for hydrogen production, also the significant effect of post treatment process was observed on the catalytic activity as given order: Co/NMs-1₄₅₀ > Co/NMs-1₂₈₉ > Co/NMs-1 > Co/NMs-1₂₃₂. Furthermore, mesoporous Co₃O₄ cubic crystals (26 nm) in fibrous architecture was prepared by 450 °C-post-treatment. Hydrogen production rates were recorded at 60 °C as 2.08, 2.20, and 6.39 l H₂.g_cat⁻¹min⁻¹ for NaBH₄, CH₃NH₂BH₃, and NH₃BH₃, respectively.     

NH3BH3/LiBH4·NH3 modified by metal hydrides for advanced dehydrogenation

The significantly enhanced dehydrogenation performance of binary complex system, NH₃BH₃/LiBH₄·NH₃, were achieved through a chemical modification of LiH to form ternary composites of x (LiH–NH₃BH₃)/LiBH₄·NH₃. Among the studied composites, 3LiH–3NH₃BH₃/LiBH₄·NH₃ released ca. 10 wt. % high-pure hydrogen (>99.9 mol%) below 100 °C with fast kinetics, while less than 8 wt. % hydrogen, accompanied with a fair number of volatile byproducts, were released from 3NH₃BH₃/LiBH₄·NH₃ at the same conditions. Further investigations revealed that the hydrogen emission from x (LiH–NH₃BH₃)/LiBH₄·NH₃ composites is based on the combination mechanism of H^δ+ and H^δ− through the interaction between LiH–NH₃BH₃ and NH₃ group in LiBH₄·NH₃, in which the controllable protic hydrogen source from the stabilized NH₃ group played a crucial role in providing optimal stoichiometric ratio of H^δ+ and H^δ−, and thus leading to the significant improvement of dehydrogenation capacity and purity.     

Combination of two H-enriched B–N based hydrides towards improved dehydrogenation properties

A new hydrogen storage system NaZn(BH₄)₃?2NH₃-nNH₃BH₃ (n = 1–5) was synthesized via a simple ball milling of NaZn(BH₄)₃?2NH₃ and NH₃BH₃ (AB) with a molar ratio from 1 to 5. Dehydrogenation results revealed that NaZn(BH₄)₃?2NH₃-nAB (n = 1–5) showed a mutual dehydrogenation improvement in terms of significant decrease in the dehydrogenation temperature and preferable suppression of the simultaneous evolution of by-products (i.e. NH₃, B₂H₆ and borazine) compared to the unitary compounds (NaZn(BH₄)₃?2NH₃ and AB). Specially, the NaZn(BH₄)₃?2NH₃-4AB sample is shown to reach the maximum hydrogen purity (99.1 mol %) and favorable dehydrogenation properties rapidly releasing 11.6 wt. % of hydrogen with a peak maximum temperature of 85 °C upon heating to 250 °C. Isothermal dehydrogenation results revealed that 9.6 wt. % hydrogen was liberated from NaZn(BH₄)₃?2NH₃-4AB within 80 min at 90 °C. High-resolution in-situ XRD and Fourier transform infrared (FT-IR) measurements indicated that the significant improvements on the dehydrogenation properties in NaZn(BH₄)₃?2NH₃-4AB can be attributed to the interaction between the NH₃ group from NaZn(BH₄)₃?2NH₃ and AB in the mixture, resulting a more activated H^δ+···^−δH combination. The research on the reversibility of the spent fuels of NaZn(BH₄)₃?2NH₃-4AB showed that regeneration could be partly achieved by reacting them with hydrazine in liquid ammonia. These aforementioned favorable dehydrogenation properties demonstrate the potential of the combined systems to be used as solid hydrogen storage material.     

Preparation and dehydrogenation properties of two cobalt-based ammine borohydrides: CoCl3·3NH3/3LiBH4 and CoCl2·3NH3/2LiBH4

Two new cobalt-based ammine borohydrides were prepared via ball milling of LiBH₄ and CoCl_n·3NH₃ (n = 3, 2) with molar ratios of 3:1 and 2:1, respectively. X-ray diffraction (XRD) results revealed the as-prepared composites having amorphous state. Thermogravimetric analysis-mass spectrometry (TG-MS) measurements showed that the two composites mainly release H₂, concurrent with the evolution of a small amount of NH₃. Further results showed that the excessive addition of LiBH₄ can suppress the liberation of NH₃, resulting in the release of H₂ with a high purity (>99 mol.%). By combination with the temperature-programmed-desorption (TPD) results, the CoCl₃·3NH₃/4LiBH₄ and CoCl₂·3NH₃/3LiBH₄composites can release 7.3 wt.% (4.2 wt.% including LiCl) and 4.2 wt.% (2.0 wt.% including LiCl) pure hydrogen, respectively, in the temperature range of 25–300 °C. Isothermal dehydrogenation results reveal that CoCl₃·3NH₃/3LiBH₄ shows favorable dehydrogenation rate at low temperatures, releasing about 5.2 wt.% (2.9 wt.% including LiCl) of hydrogen within 45 min at 80 °C.