双电子氧还原反应（2e⁻ ORR）为过氧化氢（H₂O₂）的现场制备提供了一条有前景的途径，可作为高能耗蒽醌工艺的绿色替代方案。然而，在目标2e⁻路径上，竞争性的4e⁻ ORR具有较高选择性，导致H₂O₂的法拉第效率偏低，这成为催化剂设计中的一个关键挑战。本文构建了一种锚定有Co原子的氮掺杂中空分级多孔碳材料（Co−N/HPC），用于高性能H₂O₂电合成。该Co−N/HPC催化剂展现出优异的2e⁻ ORR性能，在0.4 V（vs. RHE）的施加电位下，H₂O₂选择性接近100%。此外，原位生成的H₂O₂在降解有机污染物方面表现出高效性，展示了该材料在环境修复中的双功能特性。物理表征与模拟计算证实，性能的提升归因于独特的分级结构，该结构促进了电解质的快速扩散并提高了H₂O₂选择性。本研究为设计集高效H₂O₂生产与直接应用为一体的先进电催化剂开辟了新途径。

The two–electron oxygen reduction reaction (2e⁻ ORR) presents a promising route for the on-site production of hydrogen peroxide (H₂O₂), offering a green alternative to energy–consuming anthraquinone process. However, the high selectivity toward the competing 4e⁻ ORR over the desired 2e⁻ pathway leads to low Faradaic efficiency for H₂O₂, posing a critical challenge in catalyst design. In this work, a nitrogen–doped hollow hierarchical porous carbon with anchored Co atoms (Co−N/HPC) is constructed for high-performance H₂O₂ production. The Co−N/HPC catalyst shows excellent 2e⁻ ORR performance, achieving an H₂O₂ selectivity approaching 100% at an applied potential of 0.4 V (vs. RHE). Moreover, the in situ generated H₂O₂ proves highly effective in degrading organic pollutants, showcasing a dual-functionality for environmental remediation. Physical characterization and simulations confirm that the enhanced performance is attributed to the unique hierarchical structure, which facilitates fast electrolyte diffusion and boosts H₂O₂ selectivity. This work opens a new avenue for the design of advanced electrocatalysts that integrate efficient H₂O₂ production with direct application.