Intrinsic kinetic equation for oxygen reduction reaction in acidic media: the double Tafel slope and fuel cell applications

According to Sergio Trasatti, “A true theory of electrocatalysis will not be available until activity can be calculated a priori from some known properties of the materials.” Toward this goal, we developed intrinsic kinetic equations for the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) using as the kinetic parameters the free energies of adsorption and activation for elementary reactions. Rigorous derivation retained the intrinsic connection between the intermediates' adsorption isotherms and the kinetic equations, affording us an integrated approach for establishing the reaction mechanisms based upon various experimental and theoretical results. Using experimentally deduced free energy diagrams and activity-and-barriers plot for the ORR on Pt(111), we explained why the Tafel slope in the large overpotential region is double that in the small overpotential region. For carbon-supported Pt nanoparticles (Pt/C), the polarization curves measured with thin-film rotating disk electrodes also exhibit the double Tafel slope, albeit Pt(111) is several times more active than the Pt nanoparticles when the current is normalized by real surface area. An analytic method was presented for the polarization curves measured with H₂ in proton exchange membrane fuel cells (PEMFCs). The fit to a typical iR-free polarization curve at 80 °C revealed that the change of the Tafel slope occurs at about 0.77 V that is the reversible potential for the transition between adsorbed O and OH on Pt/C. This is significant because it predicts that the Butler–Volmer equation can only fit the data above this potential, regardless the current density. We also predicted a decrease of the Tafel slope from 70 to 65 mV dec⁻¹ at 80 °C with increasing oxygen partial pressure, which is consistent with the observation reported in literature.