Abstract
The 0reduction of O 2 at Fe 3O 4 cathodes in alkaline solutions takes place at electrode potentials where partial reduction of the hydrated Fe(III) surface layer occurs. Simultaneous electroreduction of the surface Fe(III) oxide and dioxygen suggests that octahedrally coordinated surface ferrous ions [Fe(II)OH −], are the active sites for oxygen electrocatalysis as proposed earlier for passive iron. The electroreduction of O 2 on Fe 3O 4 cathodes is a two-electron process: O 2 + H 2O + 2e − → HO 2 − + HO − Further decomposition of the intermediate peroxide is catalysed by reduced magnetite with a high turnover: 2HO 2 − → O 2 + 2HO − As a consequence of oxygen recycling the apparent number n* of electrons exchanged per oxygen molecule is strongly dependent on mass transport conditions. These results are relevant to understanding the mechanisms of reactions involved in the overall complex corrosion processes of ferrous alloys in aqueous aerated environments and in atmospheric corrosion.
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