Nitrogen‐doped porous carbon (NPC) materials have attracted increased attention for zinc‐air battery (ZAB) applications because of their comparable electrocatalytic activity to precious metals. However, few metal‐free NPC catalysts exhibit an oxygen reduction reaction performance better than Pt catalysts, together with high oxygen evolution reaction catalytic activity. Herein, an efficient oxygen electrocatalyst based on highly integrated carbon nanofiber (CNF) and NPC aerogels, with CNF as the core and NPC as the shell, is demonstrated. The NPC@CNF aerogels are prepared through a large‐scale, direct pyrolysis of metal‐organic frameworks and bacterial cellulose hybrids. This mono‐doped carbon material with nitrogen heteroatoms displays outstanding bifunctional performance compared to the individual counterparts, which demonstrates the effectiveness of morphological and structural engineering. Density functional theory calculations reveal that the active sites with the participation of multi‐electrons weaken the O−O bond and facilitate the four‐electron oxygen reduction in the dissociation pathway. The ZAB based on the NPC@CNF air electrode exhibits a peak density of 96 mW cm⁻² and a stable charge–discharge durability of over 420 cycles with an overpotential increase of only 0.10 V, indicating that the mono‐doped NPC@CNF performs as one of the best bifunctional catalysts among those recently reported metal‐based and metal‐free catalysts.

中文翻译：

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单掺杂碳纳米纤维气凝胶作为可充电锌空气电池的高性能电极材料

氮掺杂多孔碳（NPC）材料因其可与贵金属媲美的电催化活性而吸引了锌空气电池（ZAB）应用的更多关注。但是，很少有无金属的NPC催化剂具有比Pt催化剂更好的氧还原反应性能，以及高的析氧反应催化活性。在本文中，展示了一种基于高度集成的碳纳米纤维（CNF）和NPC气凝胶，以CNF为核心，NPC为壳的高效氧电催化剂。NPC @ CNF气凝胶是通过金属有机骨架和细菌纤维素杂化物的大规模直接热解制备的。与单独的同类材料相比，这种带有氮杂原子的单掺杂碳材料显示出出色的双功能性能，证明了形态学和结构工程学的有效性。密度泛函理论计算表明，多电子参与的活性位点削弱了O-O键，并促进了解离路径中四电子氧的还原。基于NPC @ CNF空气电极的ZAB的峰值密度为96 mW cm⁻²且在超过420个循环中具有稳定的充放电耐久性，并且仅在0.10 V的过电势下增加，这表明单掺杂NPC @ CNF在最近报道的基于金属和不含金属的那些中是最好的双功能催化剂之一催化剂。