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Abstract: Solid-state NaBH4/Ru-based catalyst composites have been fabricated for hydrogen generation through a high-energy ball-milling process, providing uniform dispersion of resin-supported Ru3+ catalysts among pulverized NaBH4 (SBH) particles, so as to increase the contacts of SBH with active catalytic sites. Consequently, the gravimetric hydrogen storage capacity as high as 7.3wt% could be achieved by utilizing water as a limiting reagent to overcome the issue of deactivated catalysts whose active sites are often blocked by precipitates caused by limited NaBO2 solubility occurring in conventional aqueous SBH systems for hydrogen productions. Products of hydrolyzed SBH that greatly influence the gravimetric H2 storage capacity are found to be most likely NaBO2·2H2O and NaBO2·4H2O from SBH/H2O reacting systems with initial weight ratios, SBH/H2O=1/2 and 1/10, respectively, according to the TGA and XRD analyses. [Copyright &y& Elsevier]

Abstract: A fast and simple fabrication process, viz. a wet-chemical reduction process, was utilized for preparation of a cobalt-based catalyst to be used for hydrogen generation from alkaline NaBH4 solution. Characteristics of this cobalt-based catalyst were carried out by using various instruments, such as SEM/EDS, XPS, ICP, VSM, BET and TGA. The surface chemistry of the obtained catalyst is mainly cobalt oxides, not cobalt borides. Ferromagnetic property of the cobalt-based catalyst makes it convenient for being recycled from spent NaBH4 solution. The rate of hydrogen generation from catalyzed hydrolysis of alkaline NaBH4 solution was determined as a function of temperature, NaBH4 concentration, and NaOH concentration in the presence of prepared catalysts. In general, stable generation rate of highly pure hydrogen near 200mLmin−1 g−1 was achieved in 100mL of 5wt% NaBH4 solution containing 5wt% NaOH solution and 200mg of Co/IR-120 catalyst, in which no temperature runoff was observed during the course of hydrogen production. The activation energy of NaBH4 hydrolysis reaction was found at 66.67kJmol−1, which was comparable with others reported in the open literatures. [Copyright &y& Elsevier]

Abstract: Magnetic nickel–ruthenium based catalysts on resin beads for hydrogen generation from alkaline NaBH4 solutions were synthesized with combined methods of chemical reduction and electroless deposition. Factors, such as solution temperature, NaBH4 loadings, and NaOH concentration, on performance of these catalysts on hydrogen production from alkaline NaBH4 solutions were investigated. Furthermore, characteristics of these nickel–ruthenium based catalysts were carried out by using various instruments, such as SEM/EDS, XPS, SQUID VSM and BET. These catalysts can be easily recycled from spent NaBH4 solution with permanent magnets owing to their intrinsic soft ferromagnetism and, therefore, reducing the operation cost of the hydrogen generation process. A rate of hydrogen evolution as high as ca. 400mL min−1 g−1 could be reached at 35°C in 10wt% NaBH4 solution containing 5wt% NaOH using Ni–Ru/50WX8 catalysts. Activation energy of hydrogen generation using such catalysts is estimated at 52.73kJ mol−1. [Copyright &y& Elsevier]

Abstract: Effect of limited water supply to hydrolysis of ammonia borane for hydrogen evolution is studied over the cases in which the initial molar ratio of water to ammonia borane (H2O/AB) is set at 1.28, 2.57 and 4.50. The conversion efficiency of ammonia borane to hydrogen is estimated from the accumulated volume of produced hydrogen gas and the quantitative analysis of hydrolysate by solid-state 11B NMR. Characteristics of hydrogen evolution are significantly influenced by both water dosage and injection rate of water. In the case that water is a limiting agent, namely, H2O/AB = 1.28, less hydrogen is produced than that predicted stoichiometrically. In contrast, conversion efficiency of ammonia borane reaches nearly 100% for the case with H2O/AB = 4.50. Injection rate of water to ammonia borane also affect profoundly the produced volume and production rate of hydrogen, if water is used as a limiting agent in the hydrolysis of ammonia borane. Nonetheless, boric acid and metaboric acid are found to be the dominant products in the hydrolysate from XRD, FT-IR and solid-state 11B NMR analysis. The hydrogen storage capacity using limited water supply in this work could reach as high as about 5.33 wt%, based on combined mass of reactants and catalyst. [Copyright &y& Elsevier]

Abstract: Hydrolysis of sodium borohydride (NaBH4) is a promising method for on-board hydrogen supply to polymer electrolyte membrane fuel cells (PEMFC). This article presents an attempt to design a novel solid-state NaBH4 composite, which is made up of NaBH4 powder, Co2+/IR-120 catalyst and silicone rubber, for hydrogen generator. The silicone rubber can act as a stabilizer in the solid-state NaBH4 composite because of its surface hydrophobicity leading to reduced diffusion rate of water into the composite. The solid-state NaBH4 composite can produce hydrogen stably near 25mLmin−1 for at least 2h without employment of any mechanical control system. Using the hydrogen generated from the solid-state NaBH4 composite, a 2W PEMFC stack is successfully operated to power a cellular phone. [Copyright &y& Elsevier]

Abstract: Solid-state composites of NaBH4 and Co-based catalyst have been fabricated for hydrogen generation via a novel mechanochemical technique, i.e. the high-energy ball milling, in which the gravimetric storage capacity of hydrogen has reached 6.7 wt%, meeting the 2010 target of at least 0.06 kg H2/kg set by the U.S. Department of Energy (DOE). The active catalysts used in the hydrolysis reaction of sodium borohydride for hydrogen generation are mainly cobalt oxides. Controlled addition of water, namely water used as a limiting agent, to the solid composites of NaBH4 and Co-based catalyst greatly improves the H2 storage capacity and resolved the issues of low gravimetric H2 storage in conventional aqueous system of sodium borohydride. Factors influencing the performance of hydrogen production such as amounts of H2O added, catalyst loadings and durations of ball-milling processes are investigated. Moreover the hydrolyzed products of NaBH4 and spent catalysts are analyzed as well. [Copyright &y& Elsevier]

Abstract: Ammonia borane (NH3BH3, AB), one kind of promising hydrogen storage materials, is hydrolyzed to produce hydrogen in presence of HCl, Co/IR-120 and Ru/IR-120 catalysts. The kinetics analysis of the AB hydrolysis shows that hydrogen production is of the first-order reaction in regard to both concentrations of ammonia borane and catalysts initially present, respectively. The hydrolyzate of ammonia borane after hydrogen evolution is also characterized with XRD, FT-IR and 11B NMR. Boric acid (H3BO3) is found to be the dominant product in the hydrolyzate. Besides, the produced gas is discovered to contain both hydrogen and ammonia according to the GC–MS analysis and the indophenol colorimetric analysis. A possible reaction pathway on hydrogen generation from hydrolysis of ammonia borane is, accordingly, proposed based on the existence of boric acid, hydrogen and ammonia in the products. The total life cycle of ammonia borane is also proposed to illustrate formation of different intermediates during the AB hydrolysis for hydrogen generation and a possible regeneration scheme of the spent ammonia borane. [Copyright &y& Elsevier]