Boundary‐Rich Carbon‐Based Electrocatalysts with Manganese(II)‐Coordinated Active Environment for Selective Synthesis of Hydrogen Peroxide

Coordinated manganese (Mn) electrocatalysts owing to their electronic structure flexibility, non‐toxic and earth abundant features are promising for electrocatalytic reactions. However, achieving selective hydrogen peroxide (H2O2) production through two electron oxygen reduction (2e‐ORR) is a challenge on Mn‐centered catalysts. Targeting this goal, we report on the creation of a secondary Mn(II)‐coordinated active environment with reactant enrichment effect on boundary‐rich porous carbon‐based electrocatalysts, which facilitates the selective and rapid synthesis of H2O2 through 2e‐ORR. The catalysts exhibit nearly 100 % Faradaic efficiency and H2O2 productivity up to 15.1 mol gcat−1 h−1 at 0.1 V versus reversible hydrogen electrode, representing the record high activity for Mn‐based electrocatalyst in H2O2 electrosynthesis. Mechanistic studies reveal that the epoxide and hydroxyl groups surrounding Mn(II) centers improve spin state by modifying electronic properties and charge transfer, thus tailoring the adsorption strength of *OOH intermediate. Multiscale simulations reveal that the high‐curvature boundaries facilitate oxygen (O2) adsorption and result in local O2 enrichment due to the enhanced interaction between carbon surface and O2. These merits together ensure the efficient formation of H2O2 with high local concentration, which can directly boost the tandem reaction of hydrolysis of benzonitrile to benzamide with nearly 100 % conversion rate and exclusive benzamide selectivity. Carbon‐supported manganese‐centered boundary‐rich electrocatalysts show high activity for selective H2O2 synthesis. The secondary epoxide and hydroxyl groups surrounding Mn−N3−O sites and the O2 enrichment in the curved boundaries together contribute to the activity enhancement for the targeted electrosynthesis.