The influence of pore size distribution on the oxygen reduction reaction performance in nitrogen doped carbon microspheres

Nitrogen-doped carbon microspheres with tunable porosity are investigated as electrocatalysts for the oxygen reduction reaction (ORR). The materials were synthesized by "nanocasting" involving the use of pyrrole as the carbon source and N-dopant, and porous silica microspheres as template. The engineered nitrogen-doped carbon particles combine several indispensable characteristics for a highly active metal-free carbon electrocatalyst: (i) a high content of nitrogen functionalities (∼8 wt%) mainly distributed in quaternary and pyridinic groups, which are highly active catalytic centers for the ORR reaction, and (ii) a high specific surface area (1200-1300 m 2 g −1 ). Furthermore, the porosity of the N-doped microspheres can be modulated from a micro- to a mesoporous structure, i.e. from a micropore size distribution centered at ∼1 nm to a widely accessible mesoporosity with two mesopores systems (∼3 nm and ∼14 nm). The electrocatalytic activity of the N-doped carbon microspheres in the oxygen reduction reaction (ORR) was studied in both basic and acid media. Both types of materials catalyze the ORR via the efficient 4-electron process. However, the mesoporous carbon exhibits a more positive onset potential and a higher kinetic current density than the microporous microspheres and noteworthy the values are comparable to those of commercial Pt/C under basic conditions. Moreover, the mesoporous microspheres also show a better electrocatalytic activity than the microporous ones in acid medium, and a similar onset potential to that of Pt/C with a peroxide yield lower than 10%. A detailed comparison between the N-doped micro- and mesoporous microspheres reveals that the mesoporous material outperforms the microporous one not only in catalytic activity but also in durability in both electrolytes, which proves that the bimodal mesoporous structure acts as interconnected highways providing quick and full transport towards/from the catalytic sites for both reactant and products. This leads in turn to an effective metal-free carbon catalyst that can match the commercial Pt/C catalyst. High-performance nitrogen-doped carbon electrocatalysts for the oxygen reduction reaction have been synthesized by the rational design of their pore structure.