1e:T506,Electrosynthesis of hydrogen peroxide (H₂O₂) through oxygen reduction reaction (ORR) is an environment-friendly and sustainable route for obtaining a fundamental product in the chemical industry. Co-N₄ single-atom catalysts (SAC) have sparkled attention for being highly active in both 2e^- ORR, leading to H₂O₂ and 4e^- ORR, in which H₂O is the main product. However, there is still a lack of fundamental insights into the structure-function relationship between CoN₄ and the ORR mechanism over this family of catalysts. Here, by combining theoretical simulation and experiments, we unveil that pyrrole-type CoN₄ (Co-N SAC_Dp) is mainly responsible for the 2e^- ORR, while pyridine-type CoN₄ catalyzes the 4e^- ORR. Indeed, Co-N SAC_Dp exhibits a remarkable H₂O₂ selectivity of 94% and a superb H₂O₂ yield of 2032 mg for 90 h in a flow cell, outperforming most reported catalysts in acid media. Theoretical analysis and experimental investigations confirm that Co-N SAC_Dp─with weakening O₂/HOO* interaction─boosts the H₂O₂ production.1f:T533,Abstract The electrochemical reduction of O 2 via a two‐electron reaction pathway to H 2 O 2 provides a possibility for replacing the current anthraquinone process, enabling sustainable and decentralized H 2 O 2 production. Here, a nitrogen‐rich few‐layered graphene (N‐FLG) with a tunable nitrogen configuration is developed for electrochemical H 2 O 2 generation. A positive correlation between the content of pyrrolic‐N and the H 2 O 2 selectivity is experimentally observed. The critical role of pyrrolic‐N is elucidated by the variable intermediate adsorption profiles as well as the dependent negative shifts of the pyrrolic‐N peak on X‐ray adsorption near edge structure spectra. By virtue of the optimized N doping configuration and the unique porous structure, the as‐fabricated N‐FLG electrocatalyst exhibits high selectivity toward electrochemical H 2 O 2 synthesis as well as superior long‐term stability. To achieve high‐value products on both the anode and cathode with optimized energy efficiency, a practical device coupling electrochemical H 2 O 2 generation and furfural oxidation is assembled, simultaneously enabling a high yield rate of H 2 O 2 at the cathode (9.66 mol h −1 g cat −1 ) and 2‐furoic acid at the anode (2.076 mol m −2 h −1 ) under a small cell voltage of 1.8 V.

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