Efficient Neutral H2O2 Electrosynthesis from Favorable Reaction Microenvironments via Porous Carbon Carrier Engineering

The efficient electrosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e− ORR) in neutral media is undoubtedly a practical route, but the limited comprehension of electrocatalysts has hindered the system advancement. Herein, we present the design of model catalysts comprising mesoporous carbon spheres‐supported Pd nanoparticles for H2O2 electrosynthesis at near‐zero overpotential with approximately 95 % selectivity in a neutral electrolyte. Impressively, the optimized Pd/MCS‐8 electrocatalyst in a flow cell device achieves an exceptional H2O2 yield of 15.77 mol gcatalyst−1 h−1, generating a neutral H2O2 solution with an accumulated concentration of 6.43 wt %, a level sufficiently high for medical disinfection. Finite element simulation and experimental results suggest that mesoporous carbon carriers promote O2 enrichment and localized pH elevation, establishing a favorable microenvironment for 2e− ORR in neutral media. Density functional theory calculations reveal that the robust interaction between Pd nanoparticles and the carbon carriers optimized the adsorption of OOH* at the carbon edge, ensuring high active 2e− process. These findings offer new insights into carbon‐loaded electrocatalysts for efficient 2e− ORR in neutral media, emphasizing the role of carrier engineering in constructing favorable microenvironments and synergizing active sites. The mesoporous carbon sphere carriers were optimized to enhance O2 enrichment and localized pH elevation, establishing a favorable microenvironment for 2e− ORR in neutral media to generate H2O2 with an exceptional production rate of 15.77 mol gcatalyst−1 h−1, yielding a neutral H2O2 solution suitable for medical disinfection.