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 from sodium borohydride using microreactor for micro fuel cells

A microreactor for hydrogen generation from sodium borohydride was designed and fabricated in the present study. The microreactor has three photosensitive glasses, including the cover, the reactor layer and the base. A nickel form was inserted in the reactor layer as a catalyst support. A Co-P-B catalyst for sodium borohydride hydrolysis was coated on the nickel form by electroless plating. The characteristics of the catalyst were studied using SEM and EDS analysis. The hydrogen generation rate of the microreactor was measured under a variety of conditions and made up 15.6 ml/min at a temperature of 40 °C. The generated hydrogen was supplied to a micro fuel cell with a maximum power output of 157 mW at a current of 0.5 A.     

A tank in series model for alkaline fuel cell in cogeneration of hydrogen peroxide and electricity

This work presents a Tank in Series Reactor (TSR) model for the alkaline fuel cell operating in potentiostatic mode in cogeneration of H₂O₂ and electricity. The developed TSR model accounts for the component and the energy balances in gas channels, liquid alkaline and catalyst layers together with charge balances at electrode/electrolyte interfaces. The TSR model is able to predict the limiting two-dimensional profiles in alkaline fuel cell. The simulation results indicate the influence of mass transfer on the distribution of concentration, temperature and current density.     

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.     

Hydrogen production from solid sodium borohydride with hydrogen peroxide decomposition reaction

This study investigates hydrogen production from solid sodium borohydride with hydrogen peroxide decomposition reaction for a fuel cell based air-independent propulsion system in space and underwater applications. Sodium borohydride in the solid state was used as a hydrogen source in the present study. Pure hydrogen could be generated by a catalytic hydrolysis reaction in which the water source was obtained from the hydrogen peroxide decomposition. Hydrogen peroxide was selected as an oxidizer, being decomposed catalytically to generate oxygen and water. The pure oxygen was provided to a fuel cell and the water was stored separately for the hydrolysis reaction. A fuel cell system was fabricated to validate the fuel cell based air-independent power system proposed in the present study. Two catalytic reactors were prepared; one for the solid sodium borohydride hydrolysis reaction and the other for the hydrogen peroxide decomposition reaction. The hydrogen and oxygen generation rate were measured based on the various conditions. The performance evaluation of a fuel cell system proposed in the present study was carried out.     

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.     

Electrospun carbon nanofiber-encapsulated NiS nanoparticles as an efficient catalyst for hydrogen production from hydrolysis of sodium borohydride

Carbon nanofibers (CNFs) incorporating NiS nanoparticles (NPs), namely NiS@CNFs were prepared by one-step electrospinning and successfully employed as a catalyst for hydrogen production from hydrolytic dehydrogenation of sodium borohydride (SBH). As-prepared NiS@CNFs, composed of polyacrylonitrile (PAN), nickel acetate, and ammonium sulfide, was calcined at 900 °C in argon atmosphere, and characterized using standard surface science techniques. The combined results revealed the growth of NiS NPs inside the CNFs, hence confirmed the presence of elemental Ni, S, and C. The as-prepared NiS@CNFs catalyst has a significantly higher surface area (650.92 m²/g) than the reported value of 376 m²/g. Importantly, this catalyst exhibited a much higher catalytic performance, for H₂ production from SBH, than that of Ni@CNFs, as evidenced by its low activation energy (∼25.11576 kJ/mol) and their R_max values of 2962 vs. 1770 mL/g·min. Recyclability tests on using NiS@CNFs catalyst showed quantitatively production (∼100% conversion) of H₂ from SBH and retained up to 70% of its initial catalytic activity after five successive cycles. The low cost and high catalytic performance of the designed NiS@CNFs catalyst enable facile H₂ production from readily available hydrogen storage materials.     

Influences of sodium borohydride concentration on direct borohydride fuel cell performance

In this work, the effects of sodium borohydride concentration on the performance of direct borohydride fuel cell, which consisted of Pd/C anode, Pt/C cathode and Na⁺ form Nafion^® membrane as the electrolyte, have been investigated in steady state/steady-flow and uniform state/uniform-flow systems. The experimental results have revealed that the power density increased as the sodium borohydride concentration increased in the SSSF system. Peak power densities of 7.1, 10.1 and 11.7 mW cm⁻² have been obtained at 0.5, 1 and 1.5 M, respectively. However, the performance has decreased when the sodium borohydride concentration has been increased, and the fuel utilization ratios of 29.8%, 21.6% and 20.4% have been obtained at 0.5, 1 and 1.5 M, respectively in the USUF system.     

Development of a compact hydrogen generator from sodium borohydride

Chemical hydrides can be a simple and safe hydrogen vector for polymer fuel cells. In particular the catalytic hydrolysis of sodium borohydride (NaBH₄) is here envisaged to produce on-demand hydrogen to be supplied to a small solid polymer fuel cell in a portable energy generator.     

A direct borohydride fuel cell employing Prussian Blue as mediated electron-transfer hydrogen peroxide reduction catalyst

A direct borohydride-hydrogen peroxide fuel cell employing carbon-supported Prussian Blue (PB) as mediated electron-transfer cathode catalyst is reported. While operating at 30 °C, the direct borohydride-hydrogen peroxide fuel cell employing carbon-supported PB cathode catalyst shows superior performance with the maximum output power density of 68 mW cm⁻² at an operating voltage of 1.1 V compared to direct borohydride-hydrogen peroxide fuel cell employing the conventional gold-based cathode with the maximum output power density of 47 mW cm⁻² at an operating voltage of 0.7 V. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Analysis (EDAX) suggest that anchoring of Cetyl-Trimethyl Ammonium Bromide (CTAB) as a surfactant moiety on carbon-supported PB affects the catalyst morphology. Polarization studies on direct borohydride-hydrogen peroxide fuel cell with carbon-supported CTAB-anchored PB cathode exhibit better performance with the maximum output power density of 50 mW cm⁻² at an operating voltage of 1 V than the direct borohydride-hydrogen peroxide fuel cell with carbon-supported Prussian Blue without CTAB with the maximum output power density of 29 mW cm⁻² at an operating voltage of 1 V.     

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.     

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.     

Synthesis of Ni/TiO2 catalyst by sol-gel method for hydrogen production from sodium borohydride

Hydrogen is a sustainable, renewable and clean energy carrier that meets the increasing energy demand. Pure hydrogen is produced by the hydrolysis of sodium borohydride (NaBH₄) using a catalyst. In this study, Ni/TiO₂ catalysts were synthesized by the sol-gel technique and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) methods. The effects of Ni loading ratio (20–40%), catalyst amount (75–200 mg), the concentration of sodium hydroxide (NaOH, 0.25–1 M), initial amount of NaBH₄ (75–125 mg) and the reaction temperature (20–60 °C) on hydrogen production performance were examined. The hydrogen yield (100%) and hydrogen production rate (110.87 mL/g_cat.min) were determined at the reaction conditions of 5 mL of 0.25 M NaOH, 100 mg NaBH₄, 100 mg Ni/TiO₂, 60 °C. Reaction order and activation energy were calculated as 0.08 and 25.11 kJ/mol, respectively.     

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.     

Nickel-based catalysts for hydrogen evolution by hydrolysis of sodium borohydride: from structured nickel hydrazine nitrate complexes to reduced counterparts

Nickel complexes have recently been presented as prospective catalytic materials for hydrogen H₂ evolution by hydrolysis of sodium borohydride NaBH₄. An attractive complex is nickel hydrazine nitrate [Ni(N₂H₄)₃][NO₃]₂ for which little variations in the synthesis procedure result in different morphologies like hexagonal plates, clews and discs. In our conditions, the clews have the better catalytic activity owing to more defects and more active sites. There is an effect of the morphology on the catalytic activity. However, the H₂ evolution curves (regardless the initial morphology) show an induction period during which the complex (purple violet in color) evolves into a catalytically active form (fine black powder). The evolution is featured by changes in morphology and chemical state of nickel. The catalytically active form is even more active than the pristine complex: it shows a higher H₂ generation rate (three times higher in the best case). The starting complexes and the “reduced” counterparts have been then characterized (e.g. SEM, FTIR, XRD, XPS) to better understand the aforementioned evolutions. One of our main conclusions is that there are some marked analogies between our nickel-based catalysts and the much-investigated cobalt-based catalysts.     

Cathode electrocatalyst selection and deposition for a direct borohydride/hydrogen peroxide fuel cell

Catalyst selection, deposition method and substrate material selection are essential aspects for the design of efficient electrodes for fuel cells. Research is described to identify a potential catalyst for hydrogen peroxide reduction, an effective catalyst deposition method, and supporting material for a direct borohydride/hydrogen peroxide fuel cell. Several conclusions are reached. Using Pourbaix diagrams to guide experimental testing, gold is identified as an effective catalyst which minimizes gas evolution of hydrogen peroxide while providing high power density. Activated carbon cloth which features high surface area and high microporosity is found to be well suited for the supporting material for catalyst deposition. Electrodeposition and plasma sputtering deposition methods are compared to conventional techniques for depositing gold on diffusion layers. Both methods provide much higher power densities than the conventional method. The sputtering method however allows a much lower catalyst loading and well-dispersed deposits of nanoscale particles. Using these techniques, a peak power density of 680 mW cm⁻² is achieved at 60 °C with a direct borohydride/hydrogen peroxide fuel cell which employs palladium as the anode catalyst and gold as the cathode catalyst.     

Co3O4 hollow fiber: An efficient catalyst precursor for hydrolysis of sodium borohydride to generate hydrogen

Sodium borohydride (NaBH₄) is one of promising hydrogen storage materials for practical application, and the development of high-efficient catalysts for NaBH₄ hydrolysis to generate hydrogen is of critical importance. In this communication, Co₃O₄ hollow fiber composed of nanoparticles array was served as catalyst precursor and facilely prepared by combustion method with template of the absorbent cotton. For characterization, FE-SEM, HRTEM, EDS, XRD, FTIR and ICP were applied, respectively, and typical water-displacement method was performed to evaluate the catalytic activity. Using a solution composed of 10 wt% NaBH₄ and 2 wt% NaOH, hydrogen generation rate was up to 11.12 L min^?1 g^?1 (25 °C), which is much higher than that of the commercial cobalt oxides and similar catalyst precursors reported in literature.     

Magnetically recyclable Fe@Co core-shell catalysts for dehydrogenation of sodium borohydride in fuel cells

Co-based catalysts of the reaction by which hydrogen was obtained from NaBH₄ solution were prepared by chemical reduction in a liquid phase. X-ray diffraction and scanning electron microscopy analyses showed that the as-prepared Fe@Co catalyst was ultrafine and amorphous. The calculated Arrhenius activation energy of the Fe@Co catalyst was 35.62(1) kJ mol⁻¹ while that of the Co catalyst was 38.81(2) kJ mol⁻¹, demonstrating that Fe@Co nanoparticles reduce the activation energy of the reaction more than does a Co nanocatalyst. X-ray absorption spectroscopy (XAS) clearly reveals the valences of Fe and Co. The Fe valence of Fe@Co is smallest among three catalysts because of the Co shell. The molar ration of Fe to Co is 1: 2 as determined by using XPS analysis, indicating that the novel catalyst reduces costs. The generation of hydrogen is schematically elucidated.