Defect Engineering on Commercial Carbon for Economical H ₂ O ₂ Electrosynthesis Under Industrial‐Relevant Conditions

Abstract Electrochemical H ₂ O ₂ production through two‐electron oxygen reduction reaction (2e ⁻ ORR) offers a sustainable and green alternative to the traditional anthraquinone process. However, the development of efficient catalysts that simultaneously achieve high selectivity, activity, and stability under industrially relevant production rates remains a significant challenge. This study presents a defect engineering strategy to optimize commercial Vulcan carbon for efficient H ₂ O ₂ electrosynthesis via 2e ⁻ ORR. By systematically modulating defect densities, it is identified that carbon materials with moderate defect concentrations (D10‐vulcan) achieve an optimal balance between activity and selectivity, demonstrating over 95% H ₂ O ₂ selectivity and sustained performance at 400 mA cm ⁻² for 200 h under industrial‐relevant conditions. Density functional theory (DFT) calculations reveal that edge defects and holes act as 4e ⁻ ORR active sites, while adjacent carbon atoms serve as 2e ⁻ active sites, providing a mechanistic understanding of defect‐mediated selectivity. The proposed “active site saturation” theory explains performance variations under high overpotentials and low oxygen availability, offering a scalable approach and electrocatalyst design guidance for cost‐effective H ₂ O ₂ production.