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

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.