Electrocatalysis of the Oxygen Reaction by Pyropolymers of N4 Complexes

Results of research into structural and electrocatalytic properties of metalloporphyrins and metallophthalocyanines pyrolyzed on carbon supports of various dispersion degree in the oxygen electroreduction reaction (OER) are analyzed. The pyrolysis products (pyropolymers) that form at T 800° in inert atmosphere contain centers Co(Fe)–N surrounded by carbon particles. The oxygen electroreduction reaction on pyropolymers in acid and alkali solutions is studied on a model gas-diffusion electrode and a rotating ring–disk electrode. The slopes of Tafel plots in an acid solution are 60 and 120 mV. On a disk electrode covered with a pyropolymer, the intermediate product of OER, hydrogen peroxide, is fixed on the ring electrode throughout the entire range of OER potentials. The activity of pyropolymers in the hydrogen peroxide electroreduction reaction in an acid solution is insignificant. In an acid environment, OER occurs via a parallel–successive mechanism with a slow stage of the attachment of the first electron. In alkali media, slopes of Tafel plots equal 40 and 120 mV at low and high polarizations, respectively. The amount of hydrogen peroxide fixed on the ring electrode corresponds to 2–5% of the disk electrode current. A pyropolymer is active in the hydrogen peroxide reduction. The slow stage in OER in an alkali environment is the attachment of the second electron at a low polarization and the attachment of the first electron, at a high polarization. In acid and alkali solutions a pyropolymer is methanol-tolerant.