Hydrolysis of sodium borohydride with steam

The reaction of sodium borohydride with steam produces hydrogen gas and a hydrated solid. Unlike the reaction in liquid water, up to 95% yield of hydrogen is obtained with pure steam without a catalyst. Liquid promoters (methanol and acetic acid) at concentrations of 1 mol% do not enhance the reaction rate, although acetic acid improves the hydrogen yield slightly.     

Hydrogen production from solid sodium borohydride

A system for a controlled production of hydrogen from solid NaBH₄ has been designed and built. Cartridges of catalysed or non-catalysed NaBH₄ in powder form are fed by water or catalyst solution into a reactor; the reaction is started and tuned by controlling the input water (or water/catalyst solution) flow. We designed, built and tested different reactor layouts and geometries. Tests have been carried out in order to monitor operative parameters (i.e., water flow, reactor temperature) and to evaluate their influence on hydrolysis performance. The facility allows hydrogen flow in the 5–30 L/h range for several hours. The paper reports on the experimental runs and on the main achieved goals.     

Apparatus for the production of hydrogen from sodium borohydride in alkaline solution

Extended application of hydrogen as energy carrier demands an economical, safe and reliable technology for storage. In particular, chemical hydrides appear as capable and promising to overcome the issues related to hydrogen safety and handling and to be considered competitive with respect to conventional fuels.     

Hydrogen generation utilizing alkaline sodium borohydride solution and supported cobalt catalyst

Supported Co catalysts with different supports were prepared for hydrogen generation (HG) from catalytic hydrolysis of alkaline sodium borohydride solution. As a result, we found that a γ-Al₂O₃ supported Co catalyst was very effective because of its special structure. A maximum HG rate of 220 mL min⁻¹ g⁻¹ catalyst and approximately 100% efficiency at 303 K were achieved using a Co/γ-Al₂O₃ catalyst containing 9 wt.% Co. The catalyst has quick response and good durability to the hydrolysis of alkaline NaBH₄ solution. It is feasible to use this catalyst in hydrogen generators with stabilized NaBH₄ solutions to provide on-site hydrogen with desired rate for mobile applications, such as proton exchange membrane fuel cell (PEMFC) systems.     

Kinetics of Ru-catalyzed sodium borohydride hydrolysis

Chemical hydrides have been identified as a potential medium for on-board hydrogen storage, one of the most challenging technical barriers to the prospective transition from gasoline to hydrogen-powered vehicles. Systematic study of the feasibility of the sodium borohydride systems, and chemical-hydride systems more generally, requires detailed kinetic studies of the reaction for use in reactor modeling and system-level experiments. This work reports an experimental study of the kinetics of sodium borohydride hydrolysis with a Ru-on-carbon catalyst and a Langmuir-Hinshelwood kinetic model developed based on experimental data. The model assumes that the reaction consists of two important steps: the equilibrated adsorption of sodium borohydride on the surface of the catalyst and the reaction of the adsorbed species. The model successfully captures both the reaction's zero-order behavior at low temperatures and the first-order behavior at higher temperatures. Reaction rate constants at different temperatures are determined from the experimental data, and the activation energy is found to be 66.9 kJ mol⁻¹ from an Arrhenius plot.     

Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH₄) in fuel cell fields. In this study, hydrogen production from alkaline NaBH₄ via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200–400 °C, but a high calcination temperature above 500 °C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co–B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH₄, and the hydrogen generation rate increases for lower NaBH₄ concentrations and decreases after reaching a maximum at 10 wt.% of NaBH₄.     

New reactor design for catalytic sodium borohydride hydrolysis

Hydrogen supply to a fuel cell for portable consumer products requires a simple and safe technology for its storage and on-demand production. Hydrogen production by hydrolysis of sodium borohydride solution in the presence of metal catalyst could be a promising and feasible method.     

Aluminum chloride for accelerating hydrogen generation from sodium borohydride

The present research paper reports preliminary results about the utilization of anhydrous aluminum chloride (AlCl₃) for accelerating hydrogen generation through hydrolysis of aqueous solution of sodium borohydride (NaBH₄) at 80 °C. To the best of our knowledge, AlCl₃ has never been considered for that reaction although many transition metal salts had already been assessed. AlCl₃ reactivity was compared to those of AlCl₃·6H₂O, AlF₃, CoCl₂, RuCl₃ and NiCl₂. With AlCl₃ and a NaBH₄ solution having a gravimetric hydrogen storage capacity (GHSC) of 2.9 wt.%, almost 100% hydrogen was generated in few seconds, i.e., with a hydrogen generation rate (HGR) of 354 L min⁻¹ g⁻¹(Al). This HGR is one of the highest rates ever reported. Higher HGRs were obtained by mixing AlCl₃ with CoCl2, RuCl₃ or NiCl₂. For example, the system RuCl₃:AlCl₃ (50:50 mass proportion) showed a HGR > 1000 L min⁻¹ g⁻¹(Ru:Al). The hydrolysis by-products (once dried) were identified (by XRD, IR and elemental analysis) as being Al(OH)₃, NaCl and Na₂B(OH)₄Cl and it was observed that even in situ formed Al(OH)₃ has catalytic abilities with HGRs of 5 L min⁻¹ g⁻¹(Al). All of these preliminary results are discussed, which concludes that AlCl₃ has a potential as accelerator for single-use NaBH₄-based storage system.     

Fluorinated cobalt for catalyzing hydrogen generation from sodium borohydride

The present paper reports preliminary results relating to a search for durable cobalt-based catalyst intended to catalyze the hydrolysis of sodium borohydride (NaBH₄). Fluorination of Co [Suda S, Sun YM, Liu BH, Zhou Y, Morimitsu S, Arai K, et al. Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts. Appl Phys A 2001; 72: 209–12.] has attracted our attention whereas the fluorination of Co boride has never been envisaged so far. Our first objective was to compare the reactivity of fluorinated Co with that of Co boride. We focused our attention on the formation of Co boride from fluorinated Co. Our second objective was to show the fluorination effect on the reactivity of Co. Our third objective was to find an efficient, durable Co catalyst. It was observed a limited stabilization of the Co surface by virtue of the fluorination, which made the formation of surface Co boride more difficult while the catalytic activity was unaltered. The fluorination did not affect the number of surface active sites. Nevertheless, it did not prevent the formation of Co boride. The fluorination of Co boride was inefficient. Hence, fluorination is a way to gain in stabilization of the catalytic surface but it is quite inefficient to hinder the boride formation. Accordingly, it did not permit to compare the reactivity of Co boride with that of Co.     

Sustainable hydrogen production by catalytic hydrolysis of alkaline sodium borohydride solution using recyclable Co-Co2B and Ni-Ni3B nanocomposites

In this article, we report Co-Co₂B and Ni-Ni₃B nanocomposites as catalyst for hydrogen generation from alkaline sodium borohydride. Kinetic studies of the hydrolysis of sodium borohydride with Co-Co₂B and Ni-Ni₃B nanocomposites reveal that the concentration of NaBH₄ has no effect on the rate of hydrogen generation. Hydrolysis was found to be first order with respect to the concentration of catalyst. The catalytic activity of Co-Co₂B was found to be much higher than that of Ni-Ni₃B as inferred from the activation energies 35.245 KJ/mol and 55.810 kJ/mol, respectively. Co-Co₂B nanocomposites were found to be more magnetic than Ni-Ni₃B. These catalysts showed superior recyclability with almost the similar catalytic activities for several hydrolytic cycles supporting the principles of sustainability. Co-Co₂B catalyst showed hydrogen generation rate of about 4300 mL/min/g which is comparable to most of the reported good catalysts till date.     

Stability of alkaline aqueous solutions of sodium borohydride

Experimental results regarding long-term stability of the alkaline-water borohydride solutions for hydrogen generation are presented. The influence of the concentration of sodium borohydride and sodium hydroxide on the rate of borohydride hydrolysis is analyzed at various temperatures, such as 25 °C, 40 °C, and 80 °C, and various concentrations of NaOH. The rate of hydrolysis decreases with the increase of the water to sodium borohydride mole ratio. For diluted solutions at H₂O/NaBH₄ >30, the rate of hydrolysis and hydrogen generation at a given temperature remains constant. At room temperature in 1.0 N NaOH, the degree of hydrolysis is 0.01% NaBH₄/h that meets the stability requirements for the borohydride solutions during the long-term storage.     

Cobalt (II) salts,performing materials for generating hydrogen from sodium borohydride

Hydrogen generation through sodium borohydride (NaBH₄) hydrolysis has attracted much attention. This reaction has to be catalyzed by metal-based materials. We studied the catalytic potential of cobalt (II) and (III) salts. Some of them have never been studied, and compared to e.g. cobalt nanoparticles or powder, and cobalt borides. CoCl₂ showed the best performance. In our opinion, CoCl₂ should not be dismissed from the large number of catalysts. One could conceive portable applications using CoCl₂; this is briefly discussed. CoCl₂ was compared to both commercial cobalt boride and in-situ formed (through our hydrolysis conditions) cobalt boride. Their hydrogen generation rates were 86.3, 1.0 and 1.6 L min⁻¹ g⁻¹(Co), respectively. The hydrogen generation rate of CoCl₂ is one of the highest ones reported so far. It is assumed that cobalt boride surface evolves during the reaction and depends on the hydrolysis medium features. Further studies are required to fully explain the complex reaction mechanisms.     

Nickel modified dolomite in the hydrogen generation from sodium borohydride hydrolysis

Hydrogen is expected to play an important role as an energy carrier in the world's future energy systems, as it is environmentally friendly and flexible in use. Hydrolysis of NaBH₄ is a promising and effective method, especially for fuel cells and other portable devices, thanks to hydrogen release. Therefore, catalyst research is of great importance in the development of this technology. In this study, Ni/Dolomite catalyst was synthesized by wet impregnation method and used in hydrolysis process. Additionally, the effects of reaction temperature (30–60 °C), nickel content (10–40 wt%), catalyst amount (25–125 mg), NaOH concentration (0.10–0.75 M), and an initial amount of NaBH₄ (25–125 mg) on hydrogen yield were investigated. Eventually, the catalyst with 40 wt% Ni content was assigned as the most suitable catalyst, attaining H₂ production of 100% with a rate of 88.16 mL H₂/g_cat.min at 60 °C with 5 mL of 0.25 M NaOH, NaBH₄, and Ni/Dolomite catalyst (100 mg).     

Anchored cobalt film as stable supported catalyst for hydrolysis of sodium borohydride for chemical hydrogen storage

Electrodeposition was used to deposit cobalt over polycarbonate membrane (PCM), which was used as stable supported catalyst in hydrolysis of sodium borohydride NaBH₄. We selected PCM as support owing to its lightness, easy handling, stability, and porous structure with nanosized channels. Our primary objective was to obtain a catalytic film resistant to both physical degradation and delamination while H₂ bubbled on its surface. A thin film consisting of mushroom-like cobalt nanoarchitectures were prepared. By SEM, we observed that it is strongly embedded into the PCM thickness, with the anchoring occurring through the channels. This shaped catalyst was mechanically stable and did not show degradation during the reaction. The main results are reported and discussed in details herein.     

A boron-11 NMR study of the stability of the alkaline aqueous solution of sodium borohydride that is both an indirect fuel and a direct fuel for low-temperature fuel cells

Alkaline aqueous solution of sodium borohydride NaBH₄ (denoted SB-fuel) is an indirect fuel when it is used to generate H₂ by hydrolysis, with the as-generated H₂ feeding a fuel cell, and it is a direct fuel when it is an anodic fuel of a direct fuel cell. However, SB-fuel suffers from a major drawback: NaBH₄ spontaneously hydrolyzes. Our study falls within this context. We studied the instability, at the NMR scale and over 12 weeks, of a series of SB-fuels (initial NaBH₄ concentration from 3.65 to 31.22 wt%, NaOH concentration from 1 to 16 M, and temperature between ?15 and 60 °C) to find the conditions at which SB-fuel can be stored for weeks in relative safety. We found that SB-fuel with a NaOH concentration of ≥8 M is relatively stable under cold conditions (?15 and 4 °C). In these conditions, NaBH₄ is not prevented from hydrolyzing, but the reaction is significantly mitigated. Otherwise, our study highlights the gaps in our understanding of the SB-fuel, emphasizes SB-fuel is a new concept of fuel (it should not be seen as any current fuel), and points out the challenges for attaining higher technology readiness levels.     

A highly active Co-B catalyst for hydrogen generation from sodium borohydride hydrolysis

Co-B catalysts were prepared by the chemical reduction of CoCl₂ with NaBH₄ for hydrogen generation from borohydride hydrolysis. The catalytic properties of the Co-B catalysts were found to be sensitive to the preparation conditions including pH of the NaBH₄ solution and mixing manner of the precursors. A Co-B catalyst with a very high catalytic activity was obtained through the formation of a colloidal Co(OH)₂ intermediate. The ultra-fine particle size of 10 nm accounted for its super activity for hydrogen generation with a maximum rate of 26 L min⁻¹ g⁻¹ at 30 °C. The catalyst also changed the hydrolysis kinetics from zero-order to first-order.     

Exploring the technological maturity of hydrogen production by hydrolysis of sodium borohydride

Sodium borohydride NaBH₄ (SB) has been rediscovered in the late 1990s and been presented as a promising hydrogen storage material owing to its high gravimetric hydrogen density of 10.8 wt% and ability to produce H₂ by hydrolysis at ambient conditions. This looked promising, but soon hydrolysis of SB encountered numerous obstacles. In 2015, a progress report (Int J Hydrogen Energy 2015; 40:2673–91) showed that the 2000–2014 research did not overcome all of the obstacles, making SB far from being technologically mature. Eight years have passed since 2015. Have we put more effort into all aspects relating to hydrolysis of SB? If so, do we have produced scaled-up technologies and prototypes, of which we would have a better knowledge? Have we been able to gain in technological readiness level? Answering these questions is the main objective of this article. A secondary objective is to summarize the newly acquired knowledge. Five main observations stand out. First, the 2015–2022 period is regrettably similar to the 2000–2014 since, again, catalysts have dominated the field and the other aspects (e.g. recycling of the by-product to regenerate SB, scale-up and implementation) have received little attention. Second, hydrolysis of SB still runs into numerous obstacles, some of the obstacles being known since a long time and other ones being relatively new and unknown. Third, there has been little gain in terms of technological readiness level while few research groups have shown that there is room for new ideas and innovation. Fourth, energy, exergy and economic analyses are needed to evaluate the overall cost of H₂ from SB. Fifth, SB has not effectively thought from the end user perspective. In conclusion, many obstacles remain to be overcome before hydrolysis of SB can be a commercial solution for carrying and producing H₂. However, all efforts should be dedicated to (i) construct, operate and optimize H₂ production systems (i.e. prototypes and demonstrators), (ii) handle SB at the gram-to-kilogram scale, (iii) make production of SB even more efficient, and (iv) overcome all obstacles while thinking from the end user perspective.     

Catalytic hydrolysis of sodium borohydride in an integrated reactor for hydrogen generation

Chemical hydrides, such as sodium borohydride (NaBH₄), offer promising gravimetric and volumetric hydrogen storage densities. The overall system energy density depends on the reactor performance. In this study, a novel intergrated reactor design in which catalyst bed is integrated with a heat exchanger for autothermal operation showed significant improvements in reactor performance. Over 200% enhancement in reactor throughput was achieved with the integrated reactor at 99% fuel conversion with constant reaction temperature profiles over a wide range of fuel flow rates. Impacts of improved performance on system operation and overall energy density of chemical hydride based hydrogen storage system were also discussed.     

Hydrogen generation from aqueous acid-catalyzed hydrolysis of sodium borohydride

In this study, the hydrogen feed from both Ru-catalyzed and organic acid-catalyzed hydrolysis of NaBH₄ was studied in terms of hydrogen generation rate and integrated PEMFC performance. Hydrogen feed generated from the conventional Ru-catalyzed hydrolysis of NaBH₄ caused a drastic loss of PEMFC performance. It was found that the presence of sodium ion in hydrogen feed was a main factor that increased the interfacial resistance of fuel cell and, consequently, reduced the performance. Acid-catalyzed hydrolysis with powder form of NaBH₄ was adopted in order to minimize the detrimental effect of sodium ion. The hydrogen feed from acid-catalyzed hydrolysis was quite dry so that even water vapor, the carrier of sodium ion, was not detected after condensation of hydrogen feed. It was confirmed by the several experiments that the hydrogen release rate can be controlled by varying the injection rate and concentration of aqueous acid. Various organic acids were employed in the production of hydrogen and found that acidity, acid type and chemical structure are also important factors on hydrolysis of NaBH₄. The performance from the integrated acid-catalyzed hydrogen generation system with PEMFC was quite stable and no significant loss was observed contrary to that from the integrated Ru-catalyzed hydrogen generation system–PEMFC test. This result also clarified that the detrimental effect of sodium ion could be removed by minimizing the water vapor in this manner. Based on the experiment of acid-catalyzed hydrolysis, a small-scale hydrogen-generating device was designed and fabricated, from which hydrogen release was controlled by the acid concentration and injection rate of aqueous acid solution.