LAUSR

Abstract The borohydride oxidation reaction (BOR) was characterized on the three most-studied noble metals (Au, Pt and Pd) in a range of NaBH4 concentration and temperature that enables to bridge model studies of the BOR (low concentration) to more practical ones, relevant to the direct borohydride fuel cell (DBFC) operation. BOR mechanistic insights were unveiled using the complementary techniques of rotating disk electrode cyclic voltamperometry, rotating ring-disk electrode measurements of the BH3OH− production and differential electrochemical mass spectrometry detection of H2 escape. When the concentration of sodium borohydride is brought to DBFC-like operating conditions, the H2 escape is more severe and the poisoning effect of the metal surfaces by the BOR intermediates (BHads or BH3,ads) is more significant, and stronger on Pt surfaces compared to Au and Pd ones. Even at high NaBH4 concentrations, Pd exhibits promising BOR kinetics, making of this material an interesting candidate for DBFC anode electrocatalysis. These data enabled to complement our previous kinetic model and to confirm the BH3 species oxidation pathways for NaBH4 concentrations of 5 mM and 50 mM. However, this model is incomplete for high borohydride concentrations; it does not take into account possible local pH variations and cannot explain the origin of the important reduction currents measured at high potential on the Au ring electrodes. Finally, it is shown that the BOR mechanism at Pd electrodes must take into account PdH formation and oxidation.