Precise Design of Covalent Organic Frameworks for Electrocatalytic Hydrogen Peroxide Production

Abstract Electrochemical synthesis of H2O2 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 H2O2 directly from O2 and H2O. The precise‐designed MgP‐DHTA‐COF achieves H2O2 selectivity up to 96%, high Faradaic efficiency of 91% and reliable stability for H2O2 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 H2O2 production.