Asymmetric Zn─N 2 O‐Coordinated Hydrogen‐Bonded Organic Frameworks for Electrochemical Hydrogen Peroxide Production and Wastewater Purification

ABSTRACT Hydrogen‐bonded organic frameworks (HOF) demonstrate significant potential in the electrocatalytic synthesis of hydrogen peroxide. However, their practical application is severely hindered by the uncontrollable structural evolution of their skeletons during material synthesis which poses a challenge for constructing well‐defined active sites. In this study, Zn was incorporated into the HOF to fabricate Zn‐functionalized HOF (Zn‐HOF) with asymmetric Zn─N 2 O coordination configuration. Theoretical calculations and screening reveal that compared with common transition metal (Mn, Fe, Co, Ni, and Cu) systems, this asymmetric Zn─N 2 O coordination effectively regulates the electronic structure, achieving optimal adsorption on the *OOH intermediate for the 2‐electron oxygen reduction reaction. Experiments confirm the Zn‐HOF catalyst achieves 96% maximum H 2 O 2 selectivity, enabling efficient H 2 O 2 production in unpurified tap or natural lake water with 89% Faradaic efficiency. Moreover, Zn‐HOF can degrade various antibiotic pollutants, the Zn‐HOF‐loaded sandwich reactor exhibits only 0.87 kWh·m −3 energy consumption, with its single‐electrode cost merely 1/32 that of platinum‐coated electrodes. Our work provides a viable pathway for the application of HOF‐based materials in environmental remediation.