Recent advances in covalent organic framework-based catalysts for the electrosynthesis of hydrogen peroxide

As a vital chemical with annual production exceeding 4 million tons, hydrogen peroxide (H₂O₂) plays crucial roles in industrial disinfection, environmental remediation, and chemical syntheses. The current industrial-scale production relies on the energy-intensive anthraquinone oxidation (AO) process, which requires multiple reaction steps, generates significant hazardous waste, and depends on centralized manufacturing facilities. Electrochemical routes-particularly through the two-electron oxygen reduction (2e^- ORR) and water oxidation (2e^- WOR) pathways-present a sustainable alternative by enabling decentralized H₂O₂ production using renewable electricity. This review highlights the unique advantages of covalent organic frameworks (COFs) as next-generation electrocatalysts, focusing on their precisely tunable pore environments, well-defined active sites, and exceptional stability that collectively address key challenges in electrochemical H₂O₂ synthesis. We first establish fundamental structure-activity relationships by examining mechanistic aspects of 2e^- pathways, including critical intermediates (*OOH) and selectivity-determining factors. The discussion then progresses to systematic evaluation of innovative COF design strategies: (i) metal coordination for optimized intermediate adsorption, (ii) heteroatom doping for enhanced charge distribution, (iii) defect engineering for improved mass transport, and (iv) pyrolyzed derivatives' balancing activity with stability. Finally, we identify key research frontiers-including reactor engineering for industrial-scale operation, stability enhancement under realistic conditions, and techno-economic analysis-providing actionable guidance for advancing sustainable H₂O₂ electrosynthesis technologies.