Heterogeneous and homogenous catalysts for hydrogen generation by hydrolysis of aqueous sodium borohydride (NaBH4) solutions

It is clear that in order to satisfy global energy demands whilst maintaining sustainable levels of atmospheric greenhouse gases, alternative energy sources are required. Due to its high chemical energy density and the benign by-product of its combustion reactions, hydrogen is one of the most promising of these. However, methods of hydrogen storage such as gas compression or liquefaction are not suitable for portable or automotive applications due to their low hydrogen storage densities. Accordingly, much research activity has been focused on finding higher density hydrogen storage methods. One such method is to generate hydrogen via the hydrolysis of aqueous sodium borohydride (NaBH4) solutions, and this has been heavily studied since the turn of the century due to its high theoretical hydrogen storage capacity (10.8 wt%) and relatively safe operation in comparison to other chemical hydrides. This makes it very attractive for use as a hydrogen generator, in particular for portable applications. Major factors affecting the hydrolysis reaction of aqueous NaBH4 include the performance of the catalyst, reaction temperature, NaBH4 concentration, stabilizer concentration, and the volume of the reaction solution. Catalysts based on noble metals, in particular ruthenium (Ru) and platinum (Pt), have been shown to be particularly efficient at rapid generation of hydrogen from aqueous NaBH4 solutions. However, given the scarcity and expense of such metals, a transition metal-based catalyst would be a desirable alternative, and thus much work has been conducted using cobalt (Co) and nickel (Ni)-based materials to attempt to source a practical option. "Metal free" NaBH4 hydrolysis can also be achieved by the addition of aqueous acids such as hydrochloric acid (HCl) to solid NaBH4. This review summarizes the various catalysts which have been reported in the literature for the hydrolysis of NaBH4.