Kinetics of sodium borohydride direct oxidation and oxygen reduction in sodium hydroxide electrolyte. Part I. BH4- electro-oxidation on Au and Ag catalysts

• Published in: Electrochimica acta Vol. 51; no. 25; pp. 5459 - 5467
• Main Authors: CHATENET, Marian, MICOUD, Fabrice, ROCHE, Ivan, CHAINET, Eric
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier 28.07.2006
• Subjects: Chemical Sciences; Chemistry; Electrochemistry; Exact sciences and technology; General and physical chemistry; Kinetics and mechanism of reactions; Material chemistry; Alkali metal Compounds; Gold; Catalytic reaction; Borohydride; Electrolyte solution; Electrocatalysts; Transition metal; Sodium Tetrahydroborates; Experimental study; Metal particle; Supported catalyst; Sodium hydroxide; Cyclic voltammetry; Silver; Direct oxidation; Activated carbon; Oxidative degradation; Concentrated sodium hydroxide; Chronopotentiometry; Kinetic parameter; Aqueous solution; Rate constant; Electrochemical reaction; Catalyst activity
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2006.02.015

The direct oxidation of sodium borohydride in concentrated sodium hydroxide medium has been studied by cyclic and linear voltammetry, chronoamperometry and chronopotentiometry for silver and gold electrocatalysts, either bulk and polycrystalline or nanodispersed over high area carbon blacks. Gold and silver yield rather complete utilisation of the reducer: around 7.5 electrons are delivered on these materials, versus 4 at the most for platinum as a result of the BH4- non-negligible hydrolysis taking place on this latter material. The kinetic parameters for the direct borohydride oxidation are better for gold than for silver. A strong influence of the ratio of sodium hydroxide versus sodium borohydride is found: whereas the theoretical stoichiometry does forecast that eight hydroxide ions are needed for each borohydride ion, our experimental results prove that a larger excess hydroxide ion is necessary in quasi-steady state conditions. When the above-mentioned ratio is unity (1M NaOH and 1M NaBH4), the tetrahydroborate ions direct oxidation is limited by the hydroxide concentration, and their hydrolysis is no longer negligible. The hydrolysis products are probably BH3OH- ions, for which gold displays a rather good oxidation activity. Additionally, silver, which is a weak BH4- oxidation electrocatalyst, exhibits the best activity of all the studied materials towards the BH3OH- direct oxidation.