Electrochemical production of hydrogen peroxide (H₂O₂) is a sustainable and environmentally benign process. The electrochemical oxygen reduction process (ORR) via a two electron pathway (2e^- ORR) offers a practical method for on-site H₂O₂ generation. As an earth-abundant catalyst, the cobalt-nitrogen coordinated systems integrated into the carbon matrix (Co-NC) has caused wide attention for its high activity in 2e^- ORR. Even though most of the reported Co-NC catalysts have classical planar Co-N₄ coordination, axial coordination engineering has recently emerged as an effective way to control the active sites in the axial direction by using different coordination ligands. The structure-function link between the Co-N configuration of non-planar coordination and 2e^- ORR activity is, however, not fully understood. An axial-N coordinated Co-N₅ motif embedded in hierarchically porous graphite-3R carbon (Co-N₅C) was effectively synthesized using a template-sacrificing method. The Co-N₅C has a high selectivity for 2e^- ORR and a high H₂O₂ molar production rate of up to 6.78 mol peroxide/g_catalyst/h in acidic media, both of which are better than its Co-N₄ counterpart. DFT analyses demonstrate that axial-N ligands regulated the d-band center of the Co atom in the Co-N₅C catalyst, inducing a shift in ΔG_*OOH near the Sabatier volcano plot's peak (ΔG_*OOH = 4.22 eV). This optimized the binding of the *OOH intermediate and then enhanced the protonation of *OOH to produce H₂O₂ more efficiently.

电化学生产过氧化氢（H ₂ O ₂）是一种可持续且环境友好的过程。通过双电子途径（2e ^- ORR）的电化学氧还原过程（ORR）提供了一种现场生成H ₂ O ₂的实用方法。^{作为一种地球储量丰富的催化剂，集成到碳基体中的钴-氮配位体系（Co-NC）因其在2e -} ORR中的高活性而引起了广泛关注。尽管大多数报道的 Co-NC 催化剂都具有经典的平面 Co-N ₄配位方面，近年来出现的轴向配位工程是通过使用不同的配位配体来控制轴向活性位点的有效方法。然而，非平面配位的 Co-N 构型与 2e ^- ORR 活性之间的结构-功能联系尚未完全了解。使用模板牺牲方法有效地合成了嵌入分级多孔石墨-3R碳（Co-N ₅ C）中的轴向N配位Co-N _5基序。Co-N _{5 C 对 2e} ^- ORR具有高选择性，并且 H ₂ O ₂摩尔产率高达 6.78 mol 过氧化物/g_催化剂/h 在酸性介质中，两者均优于 Co-N ₄对应物。DFT 分析表明，轴向 N 配体调节Co-N ₅ C 催化剂中 Co 原子的d能带中心，引起萨巴蒂尔火山图峰值附近Δ G _*OOH的移动(Δ G _*OOH = 4.22 eV) 。这优化了*OOH中间体的结合，然后增强*OOH的质子化以更有效地产生H ₂ O ₂。