Electro-oxidation of BH4− in dimethylsulfoxide and dimethylformamide studied by rotating disk electrode voltammetry

► BH4− oxidation in nonaqueous solvents to prevent detrimental hydrolysis to H2. ► Many nonaqueous solvents react with BH4− to produce H2 or do not solubilize it. ► Only DMSO and DMF were suitable solvents for BH4−. ► DMSO and DMF prevent bulk, not surface, BH4− decomposition to H2, but decrease electron recovery. ► MeOH does not improve electron recovery by acting as a ligand to stabilize oxidized B.