Rational Design Strategies for Covalent Organic Frameworks Toward Efficient Electrocatalytic Hydrogen Peroxide Production

Abstract

Hydrogen peroxide (H2O2) is a versatile and environmentally friendly oxidant with broad applications in industry, energy, and environmental remediation. Electrocatalytic H2O2 production via the two-electron oxygen reduction reaction (2e− ORR) has emerged as a sustainable alternative to traditional anthraquinone processes. Covalent organic frameworks (COFs), as a class of crystalline porous materials, exhibit high structural tunability, large surface areas, and chemical stability, making them promising electrocatalysts for 2e− ORR. This review systematically summarizes recent advances in COF-based electrocatalysts for H2O2 production, including both metal-free and metal-containing systems. We discuss key strategies in COF design—such as dimensional modulation, linkage engineering, heteroatom doping, and post-synthetic modification—and highlight their effects on activity, selectivity, and stability. Fundamental insights into the 2e− ORR mechanism and evaluation metrics are also provided. Finally, we offer perspectives on current challenges and future directions, emphasizing the integration of machine learning, conductivity enhancement, and scalable synthesis to advance COFs toward practical H2O2 electrosynthesis.