Precise Electronic Modulation of Thianthrene‐Cored Covalent Organic Frameworks for High‐Efficiency H ₂ O ₂ Electrosynthesis in Neutral Media

ABSTRACT Covalent organic frameworks (COFs) have emerged as tunable electrocatalysts for hydrogen peroxide synthesis via two‐electron oxygen reduction in alkaline media. However, inherent H 2 O 2 decomposition in such environments necessitates the development of neutral‐pH alternatives, which remains an unresolved challenge for COF‐based systems. Herein, this work pioneers thianthrene‐integrated COF catalysts for efficient H 2 O 2 electrosynthesis under neutral conditions. By engineering linker architectures, we constructed three COFs with comparable crystallinity, porosities, and stability, but distinct electronic states. The optimized TFPTA‐TTPE‐COF exhibits high activity with a mass activity of 11.8 A g −1 and the H 2 O 2 selectivity of 93.8%. Importantly, flow‐cell system validation demonstrates industrial‐scale productivity, achieving 4461 mmol g −1 h −1 H 2 O 2 yield at a faradaic efficiency of 79.7% under 150 mA cm −2 . Theoretical analyses establish carbon atoms within imine linkers as primary active sites, where subtle structural variations fine‐tune OOH* intermediate binding energies to govern activity and selectivity. This work provides fundamental insights into designing active COFs electrocatalysts for sustainable H 2 O 2 production.