Efforts in a large number of transition metal-carbon systems are devoted to the development of efficient catalysts for oxygen reduction reaction (ORR). However, unsatisfied O₂ adsorption and slow reduction of OH* at the active centers hinder the further development of these catalysts. We here report a gasifiable reductant strategy, of which a new Cu-based metal organic framework (MOF: termed NTU-83) nanosheet was co-pyrolyzed with melamine to produce the N-coordinated atomic Cu and multi-oxidated Cu₂₊₁O active centers on the carbon foam with ultrathin skeleton. The engineered electrons and configuration of the active centers boost the catalyst (Cu/NC-1000) to show superior ORR activity (E_1/2 = 0.85 V), excellent stability, and methanol resistance. Further modeling calculation and controlled experiments reveal that the Cu₂₊₁O species play a crucial role in kinetically accelerated adsorption and activation of O₂, while the N₄ coordinated atomic Cu facilitates fast reduction of OH*. Such characteristics endow the Zn-air battery that containing Cu/NC-1000 as air cathode to show a high peak power density (138 mW·cm⁻²), a high specific capacity of 763 mAh·g_Zn⁻¹, and outstanding long-term cycle stability. The plausible mechanism and excellent performance show that gasifiable reductant strategy opens up a new route for regulation of the electronic of active sites but also provides a candidate for the practical application in energy conversion/storage devices.

大量过渡金属-碳系统致力于开发用于氧还原反应（ORR）的高效催化剂。然而，不令人满意的O ₂吸附和活性中心OH*的缓慢还原阻碍了这些催化剂的进一步发展。我们在此报告了一种可气化的还原剂策略，其中一种新的 Cu 基金属有机骨架（MOF：称为 NTU-83）纳米片与三聚氰胺共热解以产生 N 配位原子 Cu 和多氧化 Cu ₂₊₁ O活性中心位于具有超薄骨架的碳泡沫上。设计的电子和活性中心的配置促进催化剂 (Cu/NC-1000) 显示出优异的 ORR 活性 ( E _1/2= 0.85 V)、出色的稳定性和耐甲醇性。进一步的建模计算和对照实验表明，Cu _{2+1 O 物种在 O 2}的动力学加速吸附和活化中起着至关重要的作用，而 N ₄配位原子 Cu 有助于快速还原 OH*。这些特性使得以Cu/NC-1000为空气正极的锌空气电池具有高峰值功率密度（138 mW·cm ^-2）、763 mAh·g _Zn ^{-1的高比容量}，以及出色的长期循环稳定性。合理的机理和优异的性能表明，气化还原剂策略为调节活性位点的电子开辟了一条新途径，也为能量转换/存储装置的实际应用提供了候选者。