The introduction of pyridinic nitrogen (pyri-N) into carbon-based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri-N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)-supported pyri-N-containing molecules as model catalysts; the highest activity was observed for 1,10-phenanthroline/CB. X-ray photoemission spectroscopy showed that in acidic electrolytes, both pyri-N atoms of 1,10-phenanthroline could be protonated to form pyridinium ions (pyri-NH +). In O 2-saturated electrolytes, one of the pyri-NH + species was reduced to pyri-NH upon the application of a potential; no such reduction was observed in N 2-saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri-NH + occurring simultaneously with the thermal adsorption of O 2 , as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.

Although pyridinic‐nitrogen (pyri‐N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. We report on how to prevent the deactivation based on the mechanistic understanding that O2+normalpnormalynormalrnormali-normalNnormalH++normale-→4ptO2,normala+normalpnormalynormalrnormali-normalNnormalH ${{{\rm O}}_{2}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{{\rm H}}^{+}+{{\rm e}}^{-}{\to }_{\ }^{{\rm \ }}{{\rm O}}_{2,{\rm a}}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{\rm H}}$ governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri‐NH+, leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri‐NH+ but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO2 particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.

The introduction of pyridinic nitrogen (pyri-N) into carbon-based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri-N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)-supported pyri-N-containing molecules as model catalysts; the highest activity was observed for 1,10-phenanthroline/CB. X-ray photoemission spectroscopy showed that in acidic electrolytes, both pyri-N atoms of 1,10-phenanthroline could be protonated to form pyridinium ions (pyri-NH +). In O 2-saturated electrolytes, one of the pyri-NH + species was reduced to pyri-NH upon the application of a potential; no such reduction was observed in N 2-saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri-NH + occurring simultaneously with the thermal adsorption of O 2 , as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.

Although pyridinic‐nitrogen (pyri‐N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. We report on how to prevent the deactivation based on the mechanistic understanding that O2+normalpnormalynormalrnormali-normalNnormalH++normale-→4ptO2,normala+normalpnormalynormalrnormali-normalNnormalH ${{{\rm O}}_{2}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{{\rm H}}^{+}+{{\rm e}}^{-}{\to }_{\ }^{{\rm \ }}{{\rm O}}_{2,{\rm a}}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{\rm H}}$ governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri‐NH+, leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri‐NH+ but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO2 particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.