Nitrogen-containing superporous activated carbons were prepared by chemical polymerization of aniline and nitrogen functionalization by organic routes. The resulting N-doped carbon materials were carbonized at high temperatures (600⁻800 °C) in inert atmosphere. X-ray Photoelectron Spectroscopy (XPS) revealed that nitrogen amount ranges from 1 to 4 at.% and the nature of the nitrogen groups depends on the treatment temperature. All samples were assessed as electrocatalysts for the oxygen reduction reaction (ORR) in alkaline solution (0.1 M KOH) in order to understand the role of well-developed microporosity as well as the different nitrogen functionalities on the electrocatalytic performance in ORR. It was observed that nitrogen groups generated at high temperatures were highly selective towards the water formation. Among the investigated samples, polyaniline-derived activated carbon carbonized at 800 °C displayed the best performance (onset potential of 0.88 V versus RHE and an electron transfer number of 3.4), which was attributed to the highest concentration of N⁻C⁻O sites.
Keywords: electrocatalysis; nitrogen functionalization; oxygen reduction reaction; polyaniline; porous carbons.