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 H₂O₂ 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 H₂O₂ selectivity and absolute production rates. H₂O₂ selectivity up to 95.3 % was achieved in acidic environment, whereas the largest H₂O₂ 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 H₂O₂ production catalysts.

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氮掺杂多孔碳催化剂直接电化学生产过氧化氢的结构，活性和法拉第效率

掺杂有氮的碳材料是用于电化学过氧化氢的双电子氧还原反应（ORR）的活性催化剂。然而，关于H ₂ O ₂生产中各种化学氮官能团各自作用的见解仍然很少。在这里，我们探索了一种催化活性很高的氮掺杂多孔碳材料家族，该材料是通过将有序介孔碳（CMK-3）与聚乙烯亚胺（PEI）直接热解制备的。伏安法旋转环盘分析与计时安培法在电解池中的整体电解测量相结合，显示出施加的电势，电流密度和电解质pH对H ₂ O _{2的显着影响}选择性和绝对生产率。在酸性环境中，H ₂ O _2的选择性高达95.3％，而在中性溶液中，最大的H ₂ O ₂生产率为570.1 mmol g ^-1_催化剂 h ^-1。X射线光电子能谱（XPS）分析表明，吡啶吡啶-N在酸性催化过程中起关键作用，而石墨烯-N基团在中性和碱性条件下似乎是具有催化活性的部分。我们的结果有助于理解并帮助合理设计高效的碳基H ₂ O ₂生产催化剂。