Attempts to cathodically reduce boron oxides to borohydride in aqueous solution

Sodium borohydride is being considered as a chemical hydrogen storage material (hydrogen being released through hydrolysis) and as an anodic fuel for fuel cells. However, the current cost of sodium borohydride is prohibitively high for automotive applications. Thus, there is interest in recycling the by-product of the hydrolysis or oxidation reaction, sodium metaborate. Numerous patents claim that this reaction is feasible in aqueous solution. Here, we report extensive experiments based upon methods outlined in the patents (particularly, the so-called direct reduction using high overpotential cathode materials). We also attempt to address concerns not discussed in the patents. In particular, to the authors' knowledge, previous reports have not addressed electrostatic repulsion of metaborate anion from the cathode. We further report several methods that were designed to overcome this problem: (1) use of a cathode material having a very negative potential of zero charge, (2) modification of the electrical double layer by using specifically adsorbing tetraalkylammonium hydroxides, (3) use of a rectangular wave pulse, and (4) use of chemically modified cathodes. None of these methods produced measurable quantities of borohydride. We then speculate as to why this reaction is not feasible, at least in aqueous solutions.