Covalent organic frameworks for light-driven hydrogen peroxide production: design principles and mechanistic insights

Hydrogen Peroxide (H₂O₂) is an environmentally friendly and effective oxidizing agent with wide applications in environmental treatment and industrial processes. The production of H₂O₂ from water and oxygen using solar energy represents a promising alternative to the traditional anthrahydroquinone method. Covalent organic frameworks (COFs) have recently emerged as highly efficient catalysts, achieving great effort in photocatalytic H₂O₂ generation. This review aims to highlight the latest achievements in COF-based photocatalysts for H₂O₂ production, focusing on advanced design strategies that optimize reaction pathways: oxygen reduction reaction (ORR), water oxidation reaction (WOR), and dual-channel pathway. We first elucidate the fundamental principles of photocatalytic H₂O₂ synthesis and critical factors governing reaction pathways. Then, we discuss COF innovations, including synthesis strategies, band structure optimization, and active-site implantation, that enhance charge separation, light absorption, and intermediate stabilization. Finally, we address key challenges and provide forward-looking perspectives on mechanistic probing and material design. This review establishes a structure-activity-mechanism framework to guide next-generation photocatalysts for solar H₂O₂ generation.