Kinetic effect of the ionomer on the oxygen reduction in carbon-supported Pt electrocatalysts

The mechanism of the oxygen reduction reaction (ORR) on nanoparticulated Pt/C-Nafion electrodes prepared in one step has been studied to simulate the reaction in the cathode of a Polymer Electrolyte Fuel Cell (PEFC). The kinetic parameters have been obtained by hydrodynamic polarization in O₂-saturated 0.01–1.00 M H₂SO₄ and temperatures in the range 25.0–50.0 °C. The ORR current density was maximum and practically independent of the ionomer fraction in the rage 10–55 wt% Nafion. The poorer proton conductivity for lower Nafion fractions and the formation of catalyst areas completely surrounded by Nafion together with adsorption of Pt sites by sulfonate groups for higher Nafion fractions, explain the minor ORR activity in these conditions. The ionomer influence on the O₂ diffusion at high overpotentials for Pt/C-Nafion was negligible when the Nafion content was smaller than 20 wt%. The higher kinetic current density for Pt/C-Nafion (100 mA cm⁻²) with respect to smooth Pt-Nafion (40 mA cm⁻²), together with the smaller activation energy of the former (25 ± 4 kJ mol⁻¹) with respect to the latter (42 ± 5 kJ mol⁻¹) highlighted the better properties attained by the nanosize effect. A remarkable novel result is that the reaction order of H⁺ in HClO₄ is close to unity, whereas in sulfuric acid it is significantly smaller and changes with potential, what has been related to the sulfate adsorption. The anomalous dependence of the charge transfer coefficient with temperature was then explained by the thermal change of the double layer structure and the variation of the coverage of adsorbed species on Pt. The more sensitive effect for Pt/C-Nafion than for smooth Pt-Nafion was ascribed to the stronger interaction between the components when the nanoparticles are involved.