Solid-State NaBH₄/Co Composite as Hydrogen Storage Material: Effect of the Pressing Pressure on Hydrogen Generation Rate

A solid-state NaBH4/Co composite has been employed as a hydrogen-generating material, as an alternative to sodium borohydride solutions, in the long storage of hydrogen. Hydrogen generation begins in the presence of cobalt-based catalysts, immediately after water is added to a NaBH4/Co composite, as a result of sodium borohydride hydrolysis. The hydrogen generation rate has been investigated as a function of the pressure used to press hydrogen-generating composites from a mechanical mixture of the hydride and cobalt chloride hexahydrate. The hydrogen generation rate was observed to increase with the increase of this pressure. Pre-reduction of the cobalt chloride, using a sodium borohydride solution, leveled this dependence with a two-fold decrease in the gas generation rate. According to TEM and XPS data, oxidation of the particles of the pre-reduced cobalt catalyst took place during preparation of the composites, and it is this oxidation that appears to be the main reason for its low activity in sodium borohydride hydrolysis

Magnetically Recovered Co and Co@Pt Catalysts Prepared by Galvanic Replacement on Aluminum Powder for Hydrolysis of Sodium Borohydride

Magnetically recovered Co and Co@Pt catalysts for H2 generation during NaBH4 hydrolysis were successfully synthesized by optimizing the conditions of galvanic replacement method. Commercial aluminum particles with an average size of 80 µm were used as a template for the synthesis of hollow shells of metallic cobalt. Prepared Co0 was also subjected to galvanic replacement reaction to deposit a Pt layer. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, and elemental analysis were used to investigate catalysts at each stage of their synthesis and after catalytic tests. It was established that Co0 hollow microshells show a high hydrogen-generation rate of 1560 mL·min−1·gcat−1 at 40 °C, comparable to that of many magnetic cobalt nanocatalysts. The modification of their surface by platinum (up to 19 at% Pt) linearly increases the catalytic activity up to 5.2 times. The catalysts prepared by the galvanic replacement method are highly stable during cycling. Thus, after recycling and washing off the resulting borate layer, the Co@Pt catalyst with a minimum Pt loading (0.2 at%) exhibits an increase in activity of 34% compared to the initial value. The study shows the activation of the catalyst in the reaction medium with the formation of cobalt–boron-containing active phases

Catalytic Behavior of Iron-Containing Cubic Spinel in the Hydrolysis and Hydrothermolysis of Ammonia Borane

The paper presents a comparative study of the activity of magnetite (Fe3O4) and copper and cobalt ferrites with the structure of a cubic spinel synthesized by combustion of glycine-nitrate precursors in the reactions of ammonia borane (NH3BH3) hydrolysis and hydrothermolysis. It was shown that the use of copper ferrite in the studied reactions of NH3BH3 dehydrogenation has the advantages of a high catalytic activity and the absence of an induction period in the H2 generation curve due to the activating action of copper on the reduction of iron. Two methods have been proposed to improve catalytic activity of Fe3O4-based systems: (1) replacement of a portion of Fe2+ cations in the spinel by active cations including Cu2+ and (2) preparation of highly dispersed multiphase oxide systems, involving oxide of copper