Ammonia borane decomposition in the presence of cobalt halides

In the present work we studied the effect of cobalt halides (CoF₂, CoCl₂, CoBr₂ and CoI₂; also denoted CoX₂) on the thermal decomposition of ammonia borane NH₃BH₃ (AB) over the range 25-220 °C. The reaction was followed by thermogravimetric analysis and differential scanning calorimetry. The gaseous products analyzed by gas chromatography and mass spectrometry, and the solid by-products identified by elemental analysis: powder X-ray diffraction, infrared and X-ray photoelectron spectroscopies. Compared to pristine AB, the presence of CoCl₂ and CoBr₂ reduces both the induction period of the AB decomposition and the content of unwanted borazine in the H₂ stream, whereas the presence of CoI₂ or CoF₂ has little or no effect, respectively. We propose that the positive effect of CoX₂ comes from their electronic and steric effects, and that CoCl₂ is the compound which shows the best properties relative to these effects. Herein, the roles of Co and X are discussed and a revised mechanism of the AB dehydrocoupling initiation is proposed.     

Enhanced dehydrogenation of ammonia borane by reaction with alkaline earth metal chlorides

The study of ammonia borane (AB) with controllable dehydrogenations is an active research topic for solid-state hydrogen storage materials. The present work shows that tuning the reactivity of both B–H and N–H bonds in AB by alkaline earth metal chlorides not only results in a significantly decrease in the onset dehydrogenation temperature to 40 °C but also suppresses undesirable volatile by-products due to the incorporation of alkaline earth metal chlorides in the AB dehydrogenation process. These results provide further insights into the promotion of hydrogen release from amidoboranes and related borohydride ammine complexes.     

Ammonia borane,a material with exceptional properties for chemical hydrogen storage

Ammonia borane H₃NBH₃, first reported in 1955, is isoelectronic with ethane H₃CCH₃, but it has much different properties owing to (i) the nitrogen and boron atoms (leading to a dipole moment), (ii) the protic and hydridic hydrogens, and (iii) the heteropolar dihydrogen bonding (rationalizing its solid state at ambient conditions). Ammonia borane has exceptional properties for chemical hydrogen storage and the recent years have witnessed many efforts in making it implementable for both thermolytic and hydrolytic dehydrogenations. The present article aims at (1) giving an exhaustive overview of the 1955–2016 literature dedicated to ammonia borane's fundamentals and exceptional properties, and then (2) surveying the main achievements, limitations and challenges for chemical hydrogen storage.     

Transition metal nanoparticle catalysts in releasing hydrogen from the methanolysis of ammonia borane

Ammonia borane (H₃N·BH₃, AB) is one of the promising hydrogen storage materials due to high hydrogen storage capacity (19.6% wt), high stability in solid state as well as in solution and nontoxicity. The methanolysis of AB is an alternative way of releasing H₂ due to many advantages over the hydrolysis such as having high stability against self releasing hydrogen gas. Here we review the reports on using various noble or non-noble metal(0) catalysts for H₂ release from the methanolysis of AB. Ni(0), Pd(0), and Ru(0) nanoparticles (NPs), stabilized as colloidal dispersion in methanol, are highly active and long lived catalysts in the methanolysis of AB. The catalytic activity, lifetime and reusability of transition metal(0) NPs show significant improvement when supported on the surface of solid materials. The supported cobalt, nickel, copper, palladium, and ruthenium based catalysts are quite active in H₂ release from the methanolysis of AB. Rh(0) NPs are highly active catalysts in releasing H₂ from the methanolysis of AB when confined within the void spaces of zeolite or supported on oxide nanopowders such as nanosilica, nanohydroxyapatite, nanoalumina or nanoceria. The oxide supported Rh(0) NPs can provide high activity with turnover frequency values as high as 218 min⁻¹ and long lifetime with total turnover values up to 26,000 in generation of H₂ from the methanolysis of AB at 25 °C. When deposited on carbon the bimetallic AgPd alloy nanoparticles have the highest activity in releasing H₂ through the methanolysis of AB.     

Noncatalytic hydrothermolysis of ammonia borane

Hydrolysis of ammonia borane (AB) is attractive as a chemical method for hydrogen storage. The use of catalysts is, however, usually required. In the present paper, two new methods for releasing hydrogen from AB and water are investigated which do not involve any catalyst. One method is based on combustion of AB mixtures with nanoscale aluminum powder and gelled water. It is shown experimentally that these mixtures, upon ignition, exhibit self-sustained combustion with hydrogen release from both AB and water. The other method involves external heating of aqueous AB solutions to temperatures 120 °C or higher, under argon pressure to avoid water boiling. To clarify the reaction mechanism, isotopic experiments using D₂O instead of H₂O were conducted. It is shown that heating AB/D₂O solution to temperatures 117–170 °C releases 3 equiv. of hydrogen per mole AB, where 2–2.1 equiv. originate from AB and 0.9–1 equiv. from water. The prospects of both methods for hydrogen storage are discussed.     

Ammonia borane as hydrogen storage materials

Ammonia borane is an appropriate solid hydrogen storage material because of its high hydrogen content of 19.6% wt., high stability under ambient conditions, nontoxicity, and high solubility in common solvents. Hydrolysis of ammonia borane appears to be the most efficient way of releasing hydrogen stored in it. Since ammonia borane is relatively stable against hydrolysis in aqueous solution, its hydrolytic dehydrogenation can be achieved at an appreciable rate only in the presence of suitable catalyst at room temperature. Metal(0) nanoparticles have high initial catalytic activity in releasing H₂ from ammonia borane. Thermodynamically instable metal(0) nanoparticles can kinetically be stabilized against agglomeration either by using ligands in solution or by supporting on the surface of solid materials with large surface area in solid state. Examples of both type of stabilization are presented from our own studies. The results show that metal(0) nanoparticles dispersed in solution or supported on suitable solid materials with large surface area can catalyze the release of H₂ from ammonia borane at room temperature. Dispersion of metal(0) nanoparticles, stabilized in liquid phase by anions or polymers, seems advantageous as providing more active sites compared to the metal nanoparticles supported on a solid surface. However, the supported metal nanoparticles are found to be more stable against agglomeration than the ones dispersed in liquid phase. Therefore, metal nanoparticles supported on solid materials have usually longer lifetime than the ones dispersed in solution. Examples are given from the own literature to show how to improve the catalytic activity and durability of metal nanoparticles by selecting suitable stabilizer or supporting materials for certain metal. For the time being, nanoceria supported rhodium(0) nanoparticles are the most active catalyst providing a turnover frequency of 2010 min^?1 in releasing H₂ from ammonia borane at room temperature.     

Hydrogen release by thermolysis of ammonia borane NH3BH3 and then hydrolysis of its by-product [BNHx]

Ammonia borane (AB) is one of the most attractive hydrides owing to its high hydrogen density (19.5 wt%). Stored hydrogen can be released by thermolysis or catalyzed hydrolysis, both routes having advantages and issues. The present study has envisaged for the first time the combination of thermolysis and hydrolysis, AB being first thermolyzed and then the solid by-product believed to be polyaminoborane [NH₂BH₂]_n (PAB) being hydrolyzed. Herein we report that: (i) the combination is feasible, (ii) PAB hydrolyzes in the presence of a metal catalyst (Ru) at 40 °C, (iii) a total of 3 equiv. H₂ is released from AB and PAB-H₂O, (iv) high hydrogen generation rates can be obtained through hydrolysis, and (v) the by-products stemming from the PAB hydrolysis are ammonium borates. The following reactions may be proposed: AB → PAB + H₂ and PAB + xH₂O → 2H₂ + ammonium borates. All of these aspects as well as the advantages and issues of the combination of AB thermolysis and PAB hydrolysis are discussed.     

Chemical kinetics of Ru-catalyzed ammonia borane hydrolysis

Ammonia borane (AB) is a candidate material for on-board hydrogen storage, and hydrolysis is one of the potential processes by which the hydrogen may be released. This paper presents hydrogen generation measurements from the hydrolysis of dilute AB aqueous solutions catalyzed by ruthenium supported on carbon. Reaction kinetics necessary for the design of hydrolysis reactors were derived from the measurements. The hydrolysis had reaction orders greater than zero but less than unity in the temperature range from 16 °C to 55 °C. A Langmuir–Hinshelwood kinetic model was adopted to interpret the data with parameters determined by a non-linear conjugate-gradient minimization algorithm. The ruthenium-catalyzed AB hydrolysis was found to have activation energy of 76 ± 0.1 kJ mol⁻¹ and adsorption energy of −42.3 ± 0.33 kJ mol⁻¹. The observed hydrogen release rates were 843 ml H₂ min⁻¹ (g catalyst)⁻¹ and 8327 ml H₂ min⁻¹ (g catalyst)⁻¹ at 25 °C and 55 °C, respectively. The hydrogen release from AB catalyzed by ruthenium supported on carbon is significantly faster than that catalyzed by cobalt supported on alumina. Finally, the kinetic rate of hydrogen release by AB hydrolysis is much faster than that of hydrogen release by base-stabilized sodium borohydride hydrolysis.     

Hydrolysis of solid ammonia borane

Ammonia borane NH₃BH₃ is a promising hydrogen storage material by virtue of a theoretical gravimetric hydrogen storage capacity (GHSC) of 19.5 wt%. However, stored hydrogen has to be effectively released, one way of recovering this hydrogen being the metal-catalyzed hydrolysis. The present study focuses on CoCl₂-catalyzed hydrolysis of NH₃BH₃ with the concern of improving the effective GHSC of the system NH₃BH₃-H₂O. For that, NH₃BH₃ is stored as a solid and H₂O is provided in stoichiometric amount. By this way, an effective GHSC of 7.8 wt% has been reached at 25 °C. To our knowledge, it is the highest value ever reported. Besides, one of the highest hydrogen generation rates (HGRs, 21 ml(H₂) min⁻¹) has been found. In parallel, the increases of the water amount and temperature have been studied and the reaction kinetics has been determined. Finally, it has been observed that some NH₃ release, what is detrimental for a fuel cell. To summarize, high performances in terms of GHSCs and HGRs can be reached with NH₃BH₃ and since research devoted to this boron hydride is at the beginning we may be confident in making it viable in a near future.     

High and rapid hydrogen release from thermolysis of ammonia borane near PEM fuel cell operating temperatures

Ammonia borane (NH₃BH₃, AB), containing 19.6 wt % hydrogen, is a promising hydrogen storage material for use in proton exchange membrane fuel cell (PEM FC) powered vehicles. Our experiments demonstrate the highest H₂ yield (∼14 wt %, 2.15 H₂ equivalent) values obtained by neat AB thermolysis near PEM FC operating temperatures, along with rapid kinetics, without the use of either catalyst or additives. It was also found that only trace amount of ammonia (<10 ppm) is produced during dehydrogenation reaction and spent AB products are polyborazylene-like species, which can be efficiently regenerated using currently demonstrated methods. The results indicate that our proposed method is the most promising one available in the literature to-date for hydrogen storage, and could be used in PEM FC based vehicle applications.     

Study of kinetics and thermal decomposition of ammonia borane in presence of silicon nanoparticles

Ammonia borane (AB, NH₃BH₃) is a promising material by virtue of its high gravimetric hydrogen storage capacity of 19.6 wt%. Hydrogen release from AB initiates at around 100 °C and as such is compatible to meet the present-day requirements of a PEM fuel cell. The thermal decomposition of AB is a complex process involving several reactions. Major issues include poor reaction kinetics, leading to delayed commencement of hydrogen generation i.e. long induction period, and the small amount of hydrogen released at optimal temperature. In the current paper the thermal decomposition of AB is studied at different temperatures. Further the effect of Si nanoparticles on the induction period and kinetics as well as the gas release reaction is studied in detail using different characterization techniques. It was found that the induction period reduced and the amount of gas released increased as a result of Si nanoparticle addition. This was facilitated by a reduction in the activation energy of decomposition and improved kinetics with the addition of silicon nanoparticles.     

Mechanistic insight into the promoting effect of magnesium nickel hydride on the dehydrogenation of ammonia borane

In this paper, we report an in-depth study of the post-milled 4AB/Mg₂NiH₄ sample, with a special focus on the promoting mechanism of Mg₂NiH₄ on the dehydrogenation of AB. A combination of X-ray diffraction (XRD), Fourier transformation infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) characterizations, together with selective isotopic labelling and other designed experiments, revealed that AB and Mg₂NiH₄ react with each other from the starting phase of the dehydrogenation process, which eventually results in the formation of MgNiBNH complexes. On the other hand, it was found that the reaction between AB and Mg₂NiH₄ cannot proceed directly, but requires phase transition of normal AB to its mobile phase AB* to occur first. Hence, the promoting mechanism of Mg₂NiH₄ on the dehydrogenation of AB is attributed to its promoting effect on phase transition of normal AB to AB* under mild conditions and in particular its chemical modification of AB with Mg and Ni.     

A study of catalytic hydrolysis of concentrated ammonia borane solutions

Ruthenium catalyzed ammonia borane (AB) hydrolysis using aqueous solutions in the range of 5–25 wt% were experimentally studied. The experimental apparatus also included a means for gaseous ammonia sequestration. In addition, the effects of aging on reaction rates and total H₂ conversion were investigated using AB solutions that were stored in a limited-air environment for a maximum of 67 days. The present work provides data on total H₂ conversion, chemical kinetics, solution density, pH value, byproduct solubility, ammonia generation, and long-term storage stability of concentrated aqueous AB solutions.     

Thermal decomposition of alkaline-earth metal hydride and ammonia borane composites

We demonstrate a method to improve the promising hydrogen storage capabilities of ammonia borane by making composites with alkaline-earth metal hydrides using ball-milling technique. The ball-milling for the mixtures of alkaline-earth metal hydride (MgH₂ or CaH₂) and ammonia borane (AB) yields a destabilization compared with the ingredient of the mixture, showing the hydrogen capacity of 8.7 and 5.8 mass% at easily accessible dehydrogenation peak temperatures of 78 and 72 °C, respectively, without the unwanted by-product borazine. Through detailed analyses on the dehydrogenation performance of the composite at various ratios in the hydride and AB, we proposed a different chemical activation mechanism from that in the LiH/AB and NaH/AB systems reported in a previous literature.     

Mechanistic studies of ammonia borane dehydrogenation

Ammonia borane (NH₃BH₃, AB) has received extensive attention as a potential hydrogen storage medium, however hydrogen release mechanisms from AB are not well understood. AB follows different reaction routes if the dehydrogenation occurs in solvent or solid state, but a comparative study for AB dehydrogenation in these two states is not available. In this work, a detailed study of AB dehydrogenation mechanism in diglyme and solid state is presented, and a comprehensive reaction network for both cases is proposed. The experimental and DFT results suggest that two main reaction pathways occur; one involves cyclization of monomers which results in faster dehydrogenation at lower temperature, while the other involves propagation to acyclic intermediates which requires higher temperature to carry out the cyclization step. AB dehydrogenation in solid state was experimentally found to be initiated by B–N bond cleavage and not by direct dehydrogenation, which agrees with high level CCSD(T)/MP2 calculations reported previously. It was found that diglyme plays a significant role in hindering B–N bond cleavage of AB which facilitates the cyclization pathway. In solid state, experiments including labeled AB (ND₃BH₃) mapped out the source of hydrogen (from hydridic or protonic ends), and a clear difference in the degree of dehydrogenation from the two ends is demonstrated.     

High and rapid hydrogen release from thermolysis of ammonia borane near PEM fuel cell operating temperatures: Effect of quartz wool

Ammonia borane (NH₃BH₃, AB), containing 19.6 wt% hydrogen, is a promising hydrogen storage material for use in proton exchange membrane fuel cell (PEM FC) powered vehicles. We recently demonstrated that using quartz wool, the highest H₂ yield (2.1–2.3H₂ equivalent) values were obtained by neat AB thermolysis near PEM FC operating temperatures, along with rapid kinetics, without the use of either catalyst or chemical additives. It was found that quartz wool minimizes sample expansion and facilitates the production of diamoniate of diborane (DADB), which is a key intermediate for the release of hydrogen from AB. It was also found that only trace amount of ammonia (<10 ppm) is produced during dehydrogenation reaction and spent AB products are found to be polyborazylene-like species, which can be efficiently regenerated using currently demonstrated methods. The results indicate that our proposed method is the most promising one available in the literature to-date for hydrogen storage, and could be used in PEM FC based vehicle applications.     

A simple preparation method of sodium amidoborane, highly efficient derivative of ammonia borane dehydrogenating at low temperature

The present work reports the straightforward preparation of sodium amidoborane NaNH₂BH₃, an ammonia borane derivative (NH₃BH₃). NaNH₂BH₃ is a promising solid-state hydrogen storage material, known to dehydrogenate in milder conditions than its parent compound. The preparation was made from sodium hydride NaH and NH₃BH₃ according to three different energy-efficient routes: namely, ball-milling, grinding in a mortar, and simple mixing with a spatula. In each case, NaNH₂BH₃ was formed. In other words, it has been demonstrated that the solid-solid reaction between NaH and NH₃BH₃ can take place by simple contact of these molecules, owing to the basic character of the former and the acidity of the latter. The as-formed materials dehydrogenate to a high extent at low temperature, with ca. 2 equivalent hydrogen H₂ (NH₃-free in our conditions) evolving at temperatures up to 95 °C. An effective gravimetric hydrogen density of ca. 7.4 wt% was calculated, which may correspond to an effective capacity of 3.7 wt% (assuming the weight of NaNH₂BH₃ amounts to 50% of the weight of the whole storage system). Such performance confirms the high potential of amidoboranes as hydrogen storage material, especially when compared to NH₃BH₃.     

Room-temperature hydrogen release from activated carbon-confined ammonia borane

In chemical hydrogen storage, nanoconfinement (or nanoscaffolding) is an efficient approach to reduce the size of the particles of boron hydrides such as ammonia borane (AB, NH₃BH₃) at nanoscale while destabilizing its molecular network. It involves the dehydrogenation of AB at temperatures lower than 100 °C and hinders the formation of undesired gaseous by-products such as borazine. Herein, commercial activated carbon (AC) with a specific surface area of 716 m² g⁻¹ and a porous volume of 0.36 cm³ g⁻¹ was used as host material for AB nanoconfinement. A composite activated carbon-ammonia borane (AC@AB) was successfully prepared by infiltration in cold conditions (0 °C). Its dehydrogenation was followed by volumetric method, FTIR, XRD, TGA, DSC, GC–MS and ¹¹B MAS NMR. The most striking result is that the nanoconfined AB, being highly destabilized, dehydrogenates in ambient conditions, even at 3–4 °C. It is demonstrated that dihydrogen is formed according to two pathways that simultaneously take place. The first one is the dehydrogenation through inter- and/or intra-molecular reactions between protonic H and hydridic H of AB, and the second one is the acid-base reaction between protonic H of COO−H groups present on the AC surface and hydridic H of AB.     

Magnetically separable transition metal nanoparticles as catalysts in hydrogen generation from the hydrolysis of ammonia borane

It reviews the available reports on the preparation and use of magnetically separable transition metal nanoparticles (TMNs) as reusable catalysts for the hydrolytic dehydrogenation of ammonia borane (AB). After a short introduction, the review starts with the papers on the employment of intrinsically magnetic TMNs as catalysts for releasing H₂ gas from AB, which includes colloidal nanoparticles of intrinsically magnetic metals, TMNs in combination with materials having large surface area, and multimetallic composites containing at least one intrinsically magnetic metal together with an additional component usually acting as support or stabilizer. This is followed by a section reviewing the papers on core-shell multimetallic nanoparticles with one intrinsically magnetic metal in either core or shell used for catalyzing the hydrolysis of AB. It follows the review of papers on TMNs supported on Fe₃O₄, CoFe₂O₄, or Co₃O₄ forming magnetically separable catalysts for the same reaction. Then, a short section reviews the available reports on metal nanoparticles supported on carbon-coated iron. The last section gives a summary list of conclusions.