In the past three years, two novel synthesis methods for non-precious metal catalysts resulting in a breakthrough of their activity and performance at the cathode of the proton-exchange membrane fuel cell (PEMFC) have been reported by the group of Prof. Dodelet. While the activity of these novel Fe-based catalysts for the oxygen reduction reaction is very high in PEMFC, our preliminary activity measurements with the rotating disk electrode (RDE) technique on one of them showed an activity being a factor 30–100 lower than the one measured in PEMFC at 80 °C.
The present work explains to a large extent this huge difference. Two FeNC catalysts synthesized via our novel approaches and one FeNC catalyst synthesizedvia our classical approach were investigated in RDE and PEMFC. In both systems, the effect of the ink formulation (Nafion-to-catalyst ratio) was investigated. Optimization of the RDE ink formulation explains a factor between 5 and 10 in the two-decade gap mentioned above. Then, the effect of temperature in the RDE system was investigated. An increase from 20 to 80 °C was found to result in a theoretical maximum twofold increase in activity. However, in practice, decreased O2 solubility with increased temperature cancels this effect.
After taking into account these two parameters, a difference in ORR activity between RDE and PEMFC of ca a factor five still remained for one of the two novel FeNC catalysts investigated here. The lower initial activity measured in RDE for this catalyst is shown to be due to the fast adsorption of anions (HSO4−) from the liquid H2SO4electrolyte on protonated nitrogen atoms (NH+) found on its surface. The phenomenon of anion adsorption and associated decreased ORR activity also applies to the other novel FeNC catalyst, but is slower and does not immediately occur in RDE.