Understanding the intrinsic nature of carbon edges toward the electrocatalytic reduction of O₂ to H₂O₂ is challenging due to the inevitable coexistence of edges and heteroatom groups. Herein, ten different gradient nanocarbons with well-defined edge topologies and sizes are used as models to investigate the explicit function of each common edge at a molecular level. We suggest that both armchair and zigzag configurations are positive in H₂O₂ formation. Direct proportional structure-function relationships between the size/number/areas of edges and the activities are then proposed. Moreover, the dynamic evolution processes and kinetic behaviors of key intermediate products including O₂ (ads) and superoxide anion ${\text{O}}_2^{-\ast }$ are monitored with time-resolved infrared spectroscopy and simulation calculations. Depending on different edge configurations, O₂ (ads) and ${\text{O}}_2^{-\ast }$ species show a steep growth trend in the first 7.3 and 10 s and reach equilibrium until 10 and 13.3 s, respectively. O₂ (ads) + e^- → ${\text{O}}_2^{-\ast }$ as a possible rate-determining step (RDS) is evidenced by isotopic-labeling studies.

由于边缘和杂原子基团不可避免地共存，因此了解碳边缘对 O 2 电催化还原为 H 2 O 2 的_内在性质_具有挑战性_。在此，十种具有明确边缘拓扑和尺寸的不同梯度纳米碳被用作模型，以在分子水平上研究每个共同边缘的显式函数。我们建议扶手椅和之字形配置在 H ₂ O ₂形成中都是积极的。然后提出了边缘的大小/数量/面积与活动之间的直接比例结构-功能关系。_{此外，包括O 2}在内的关键中间产物的动态演化过程和动力学行为(ads) 和超氧阴离子${\text{○}}_2^{-*}$用时间分辨红外光谱和模拟计算监测。根据不同的边缘配置，O ₂（广告）和${\text{○}}_2^{-*}$物种在最初的 7.3 和 10 秒内呈急剧增长趋势，并分别在 10 和 13.3 秒达到平衡。O ₂ (广告) + e ^- →${\text{○}}_2^{-*}$同位素标记研究证明了一个可能的速率决定步骤 (RDS)。