Techn. Hochsch., Diss., 2002--Aachen.

Techn. Hochsch., Diss., 2005--Aachen.

The development of new storage materials will facilitate the use of hydrogen as a major energy carrier in near future. Among the chemical hydrides used as hydrogen storage materials for supplying hydrogen at ambient temperature, sodium borohydride seems to be an ideal one because it is stable under ordinary conditions and liberates hydrogen gas in a safe and controllable way in aqueous solutions. However, self hydrolysis of sodium borohydride is so slow that requires a suitable catalyst. This work aims the use of water dispersible cobalt(0) nanoclusters having large portion of atoms on the surface as catalyst for the hydrolysis of sodium borohydride. In-situ formation of cobalt(0) nanoclusters and catalytic hydrolysis of sodium borohydride were performed starting with a cobalt(II) chloride as precursor and sodium borohydride as reducing agent and substrate in the presence of a water soluble stabilizer. As stabilizer, water soluble polyacrylic acid as well as hydrogen phosphate ion were tested. Cobalt(0) nanoclusters were characterized by using all the available analytical methods including FT-IR, TEM, XPS, UV-visible electronic absorption spectroscopy. The kinetics of cobalt(0) nanoclusters catalyzed hydrolysis of sodium borohydride were studied depending on the catalyst concentration, substrate concentration, stabilizing agent concentration and temperature.

The development of new storage materials will facilitate the use of hydrogen as a major energy carrier in near future. In hydrogen economy, chemical hydrides such as NaBH4, KBH4, LiH, NaH have been tested as hydrogen storage materials for supplying hydrogen at ambient temperature. Among these chemical hydrides, sodium borohydride seems to be an ideal hydrogen storage material because it is stable under ordinary conditions and liberates hydrogen gas in a safe and controllable way in aqueous solutions. However, self hydrolysis of sodium borohydride is so slow that it requires a suitable catalyst. All of the prior catalysts tested for the hydrolysis of sodium borohydride are heterogeneous and, therefore, have limited activity because of the small surface area. Here, we report for the first time the employment of water dispersible metal(0) nanoclusters having a large portion of atoms on the surface as a catalyst for the hydrolysis of sodium borohydride. In-situ formation of nickel(0) nanoclusters and catalytic hydrolysis of sodium borohydride were performed in the same medium. Nickel(0) nanoclusters are prepared from the reduction of nickel(II) acetylacetonate by sodium borohydride in aqueous solution and stabilized with hydrogenphosphate anions. The nickel(0) nanoclusters were characterized by using XPS, Powder XRD, FT-IR, UV-Vis and NMR spectroscopic methods. The kinetics of the nickel(0) nanoclusters catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration, stabilizing agent concentration and temperature. Tha kinetic study shows that the nickel(0) nanocluster-catalyzed hydrolysis of sodium borohydride is first order with respect to catalyst concentration and zero order with respect to substrate concentration The activation parameters of this reaction were also determined from the evaluation of the kinetic data. The hydrogenphosphate-stabilized nickel(0) nanoclusters provide a lower activation energy (Ea= 55 kJ/mol) than bulk nickel (Ea=73 kJ/mol) for the hydrolysis of sodium borohydride.