Dynamic Protonation on an Amino‐Containing Quinone‐Covalent Organic Framework Enables Efficient Neutral Electrosynthesis of H 2 O 2

Abstract The electrosynthesis of hydrogen peroxide (H 2 O 2 ) in neutral media is highly desirable for sustainable applications but is fundamentally limited by insufficient proton supply. Herein, we report a quinone‐based covalent organic framework (Q‐COFs) engineered with aromatic amino groups (TfpBQ) enables efficient neutral electrosynthesis of H 2 O 2 , achieved by the synergism between Q and amino groups. The amino groups serve as dynamic proton relays, boosting the interfacial proton‐coupled electron transfer (I‐PCET) kinetics of the Q redox couples, as evidenced by a high apparent rate constant ( k app ) of 1.97×10 4 s −1 , which is 43% and 92% higher than that of the imine‐ and amide‐containing Q‐COFs, respectively. Consequently, TfpBQ achieves a remarkable H 2 O 2 yield of 19.3 mol g −1 h −1 with a Faradaic efficiency (FE) of 95.6% at 120 mA cm −2 in a neutral electrolyte, while demonstrating exceptional stability during 60‐h of continuous operation. Combined experimental and theoretical analyses demonstrate that the dynamic protonation of aromatic amino groups reconstructs the interfacial hydrogen‐bond network, enabling a sustained proton supply to the adjacent Q/H 2 Q redox cycle, which in turn optimizes the overall 2e – ORR pathway. This work underscores the importance of managing dynamic protonation in electrocatalysts design for reactions occurring in proton‐deficient microenvironment.