Tailoring Selectivity of Electrochemical Hydrogen Peroxide Generation by Tunable Pyrrolic‐Nitrogen‐Carbon

Abstract The electrochemical reduction of O₂ via a two‐electron reaction pathway to H₂O₂ provides a possibility for replacing the current anthraquinone process, enabling sustainable and decentralized H₂O₂ production. Here, a nitrogen‐rich few‐layered graphene (N‐FLG) with a tunable nitrogen configuration is developed for electrochemical H₂O₂ generation. A positive correlation between the content of pyrrolic‐N and the H₂O₂ 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 H₂O₂ 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 H₂O₂ generation and furfural oxidation is assembled, simultaneously enabling a high yield rate of H₂O₂ 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.