Kinetic and mechanistic evaluation of tetrahydroborate ion electro-oxidation at polycrystalline gold

Abstract

The anodic oxidation of tetrahydroborate ion is studied in NaOH at stationary and rotating polycrystalline Au disk electrodes. Linear sweep and cyclic voltammetry are applied varying the scan and rotation rate from 0.005 to 51.200 V s −1 and from 52.3 to 314.1 rad s −1, correspondingly. The effects of variation of BH 4 − and NaOH concentrations as well as of the potential limits of the ranges studied have been initially followed. Most of the experiments have been carried out with 10.9 mM NaBH 4 in 1.04 M NaOH at 293 K in the potential range from −1.300 to 0.900 V (vs. Ag /AgCl). It is found that 6 electrons are exchanged in the overall oxidation transformation. The kinetic analysis of the processes determining the two anodic peaks recorded under static conditions at scan rates lower than 0.500 V s −1 shows that 1.4 electrons are exchanged in the potential range of the first one (at ca −0.5 V), while the rate of the second one (at ca +0.3 V) is determined by a quasi-reversible 1-electron transfer reaction. A kinetic evidence for the participation of surface bound intermediates in the electro-oxidation process is provided. Two additional well outlined anodic peaks are recorded in the aforementioned potential range under specific experimental conditions. A quasi-8 electron mechanism involving four oxidation and hydrolysis steps is advanced to explain the experimental results. It accounts for the involvement of borohydride oxidation species and the Au +/Au 3+ mediator couple.