Precise Design of Covalent Organic Frameworks for Electrocatalytic Hydrogen Peroxide Production

Electrochemical synthesis of H 2 O 2 with high productivity is a significant challenge in electrocatalysis. Herein, we develop Mg‐ion contained covalent organic frameworks (MgP‐DHTA‐COF), comprising stacked 2D layers, well‐defined skeletons, and well‐ordered monodispersed active sites, for the electrocatalytic production of H 2 O 2 directly from O 2 and H 2 O. The precise‐designed MgP‐DHTA‐COF achieves H 2 O 2 selectivity up to 96%, high Faradaic efficiency of 91% and reliable stability for H 2 O 2 synthesis in 0.10 mol L −1 KOH aqueous solution. Both experiments and simulations demonstrate that the pyrrolic‐N fixed Mg ions in the knots promote the reactivity of COF and enhance the adsorption ability of OOH*. This work provides a valuable example for the design of an efficient electrocatalyst based on COFs for H 2 O 2 production.