Hydriding behavior in Zr-based AB2 alloy by gas atomization process

The hydriding characteristics of Zr-based AB₂ alloy produced by gas atomization have been investigated during its absorption–desorption reaction with hydrogen gas. Its gas-phase hydrogenation properties are different from those of specimens prepared by conventional methods. For the particle morphology of the as-cast and gas-atomized powders, it can be seen that the mechanically crushed powders are irregular, while the atomized powder particles are spherical. In PCT (Pressure–Composition–Temperature) measurements, for the gas-atomized particles smaller than 50 μm, the hydrogen storage capacity is dramatically decreased and the hysteresis loop becomes larger than that of the gas-atomized particles larger than 50 μm. In addition, the increase of jet pressure of gas atomization results in the decrease of hydrogen storage capacity and the slope of plateau pressure significantly increases. TEM and EDS studies showed the increase of jet pressure in the atomization process accelerated the phase separation within grain of the gas-atomized alloy, which brought about a poor hydrogenation property. In the measurements of hydrogen absorption–desorption kinetics, the improvement of desorption kinetics of gas-atomized AB₂ alloys was mainly caused by the higher plateau pressure, which is attributed to the smaller grain size and higher site energy for hydrogen in the gas-atomized alloys.     

Production of hydrogen from purge gases of ammonia plants in a catalytic hydrogen-permselective membrane reactor

The present study investigates hydrogen production in a hydrogen-permselective membrane reactor from purge gases of an ammonia plant. Hydrogen which initially exists in the purge gases and hydrogen that is produced from decomposition of ammonia on nickel–Alumina catalyst bed simultaneously permeate from reaction side to shell side through a thin layer of palladium–silver membrane. A sweep gas can be used in the shell side for increasing driving force. The amount of hydrogen that can be gained annually and effect of pressure, temperature, thickness of Pd–Ag layer, configuration of flow in the membrane reactor and sweep gas flow ratio have been studied. This study shows that the countercurrent mode is better than co-current mode of operation. The rate of hydrogen permeation increases with increasing of temperature, pressure and sweep gas flow rate. This approach produces and separates large amounts of hydrogen and decreases environmental impacts owing to ammonia emission.     

Hydrogen storage in dinuclear Pt(II) metallacycles

Hydrogen gas physisorption in two distinct dinuclear Pt(II) metallacycles was investigated with ²H nuclear magnetic resonance (NMR) spectroscopy. Hydrogen adsorption isotherm data and ²H NMR spectroscopy indicated that hydrogen storage occurs via condensation within the cavities of one of the macrocycles and at the interstitial sites in the other. In addition, this study further supports the notion that heat of adsorption and pore size play critical roles in hydrogen storage.     

Comparison of different copper–chlorine thermochemical cycles for hydrogen production

Copper–chlorine thermochemical cycles for hydrogen production are very promising water splitting cycles. In this paper, different types of copper–chlorine cycles with various numbers of steps are compared. The factors that determine the number and effective grouping of steps are analyzed. It is found that the water requirement in the hydrolysis step is affected by a combination of drying and hydrolysis steps. It is also found that hydrogen can be produced either from electrolysis of cuprous chloride, or from chlorination of copper by hydrogen chloride, which indicates a potential combination of disproportionation and chlorination steps. The major engineering advantages and disadvantages of these cycle variations with different amounts of steps will be analyzed and discussed.     

Synthesis of iron nanoparticle: Challenge to determine the limit of hydrogen reduction in supercritical water

Supercritical hydrothermal syntheses of metal nanoparticles were investigated. Organic metal salt and hydrogen gas produced by water catalyzed decomposition of formic acid was employed as metal sources and reduction agent, respectively. The formation of iron was verified by measuring the magnetic property of the products by superconducting quantum interference device (SQUID) magnetometer as well as crystallographic analysis by X-ray diffraction (XRD). As predicted by the free energy calculation of reduction of metal oxides by hydrogen molecule, silver, palladium, copper, nickel and cobalt nanoparticles were synthesized without using surface modifier, whereas, iron could be synthesized at small yield. The main product was iron oxides (mainly magnetite). In order to increase the yield of iron, hexanoic acid was employed as an in situ surface modifier of the synthesis. The surface modification lessened the size of the synthesized nanoparticles and increased the yield of iron. The optimum condition for iron synthesis was also investigated, as a result, 7.6% yield of iron was achieved.     

Co and Ni supported on CeO2 as selective bimetallic catalyst for dry reforming of methane

Co/CeO₂ (Co 7.5 wt.%), Ni/CeO₂ (Ni 7.5 wt.%) and Co–Ni/CeO₂ (Co 3.75 wt.%, Ni 3.75 wt.%) catalysts were prepared by surfactant assisted co-precipitation method. Samples were characterized by X-Ray diffraction, BET surface areas measurements, temperature programmed reduction and tested for the dry reforming of methane CH₄ + CO₂ → 2CO + 2H₂ in the temperature range 600–800 °C with a CH₄:CO₂:Ar 20:20:60 vol.% feed mixture and a total flow rate of 50 cm³ min⁻¹ (GHSW = 30,000 mL g⁻¹ h⁻¹). The bimetallic Co–Ni/CeO₂ catalyst showed higher CH₄ conversion in comparison with monometallic systems in the whole temperature range, being 50% at 600 °C and 97% at 800 °C. H₂/CO selectivity decreased in the following order: Co–Ni/CeO₂ > Ni/CeO₂ > Co/CeO₂. Carbon deposition on spent catalysts was analyzed by thermal analysis (TG-DTA). After 20 h under stream at 750 °C, cobalt-containing catalysts, Co/CeO₂ and Co–Ni/CeO₂, showed a stable operation in presence of a deposited amorphous carbon of 6 wt.%, whereas Ni/CeO₂ showed an 8% decrease of catalytic activity due to a massive presence of amorphous and graphitic carbon (25 wt.%).     

Strategies for stationary and portable fuel cell markets

In the future, hydrogen-based stationary and portable fuel cell systems can help supply some or all of the power demanded with additional advantages of higher reliability, lower emissions, independence from the general grid, and cogeneration capability. In order to understand how to prepare the future for this technology, this paper describes a thorough investigation of past alternative stationary and portable power projects in order for an assessment of the opportunities for stationary and portable fuel cell markets, as well as interactions with transportation hydrogen systems. The lessons learned from the programs are used to establish best practices and recommendations for a hydrogen strategy that addresses opportunities for hydrogen in power generation systems, as well as to make recommendations for market transformation within the hydrogen fuel cell industry.     

One-step electroless deposition of Pd/Pt bimetallic microstructures by galvanic replacement on copper substrate and investigation of its performance for the hydrogen evolution reaction

A facile and one-step method for fabrication of Pd/Pt bimetallic microstructure using galvanic replacement reaction is presented. This electroless deposition was performed without any additive reagent via simple immersion of the copper sheet in cation aqueous solution of Pd and Pt. The as-prepared electrode was characterized by using the techniques of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and cyclic voltammetry and tested for the hydrogen evolution reaction (HER) in the acidic media. Comparison of the HER on the Pd/Pt bimetallic catalysts with different Pd:Pt percentage compositions indicated that the Pd₆₀Pt₄₀ catalyst had the highest HER activity among all the Pd/Pt catalysts and a better performance than the pure Pt. The effects of galvanic replacement time and concentration of H₂SO₄ on the catalytic activity of as-prepared electrode for HER were comparatively investigated.     

Evaluation of hydrogen sorption models for AB5-type metal alloys by employing a gravimetric technique

This paper is concerned with hydrogen absorption and desorption in AB₅-type hydrogen storage metal alloys. We give a brief overview on models which have been proposed for hydrogen sorption in metals over the past decades. We choose three models based on different perspectives, i.e. thermodynamics, reaction kinetics, and mere observation (empiricism), and evaluate their applicability in order to describe the sorption behaviour. Additionally, we propose a model which is based on a cumulative distribution function. In order to evaluate the models, the hydrogen absorption and desorption isotherms of LaNi₅ and LaNi_4.5Co_0.5 are measured by means of a gravimetric technique. A nonlinear regression is performed to fit the models to experimental data. The computed model parameters are compared to values reported in the literature. The emphasis is given to the applicability of the models with respect to describing the non-ideality of the plateau region and the continuity/smoothness of phase transition regions.     

Genome based metabolic flux analysis of Ethanoligenens harbinense for enhanced hydrogen production

Ethanoligenens harbinense is a promising hydrogen producing microorganism due to its high inherent hydrogen production rate. Even though the effect of media optimization and inhibitory metabolites has been studied in order to improve the hydrogen productivity of these cultures, the identification of the underlying causes of the observed changes in productivity has not been targeted to date. In this work we present a genome based metabolic flux analysis (MFA) framework, for the comprehensive study of E. harbinense in culture, and the effect of inhibitory metabolites and media composition on its metabolic state. A metabolic model was constructed for E. harbinense based on its annotated genome sequence and proteomic evidence. This model was employed to perform MFA and obtain the intracellular flux distribution under different culture conditions. These results allow us to identify key elements in the metabolism that can be associated to the observed production phenotypes, and that can be potential targets for metabolic engineering in order to enhanced hydrogen production in E. harbinense.