Structure, Activity, and Faradaic Efficiency of Nitrogen‐Doped Porous Carbon Catalysts for Direct Electrochemical Hydrogen Peroxide Production

Carbon materials doped with nitrogen are active catalysts for the electrochemical two-electron oxygen reduction reaction (ORR) to hydrogen peroxide. Insights into the individual role of the various chemical nitrogen functionalities in the H₂ O₂ production, however, have remained scarce. Here, we explore a catalytically very active family of nitrogen-doped porous carbon materials, prepared by direct pyrolysis of ordered mesoporous carbon (CMK-3) with polyethylenimine (PEI). Voltammetric rotating ring-disk analysis in combination with chronoamperometric bulk electrolysis measurements in electrolysis cells demonstrate a pronounced effect of the applied potentials, current densities, and electrolyte pH on the H₂ O₂ selectivity and absolute production rates. H₂ O₂ selectivity up to 95.3 % was achieved in acidic environment, whereas the largest H₂ O₂ production rate of 570.1 mmol g⁻¹ catalyst h⁻¹ was observed in neutral solution. X-ray photoemission spectroscopy (XPS) analysis suggests a key mechanistic role of pyridinic-N in the catalytic process in acid, whereas graphitic-N groups appear to be catalytically active moieties in neutral and alkaline conditions. Our results contribute to the understanding and aid the rational design of efficient carbon-based H₂ O₂ production catalysts.