A diode‐inspired microenvironment enables efficient direct <scp> H ₂ O ₂ </scp> synthesis from <scp> H ₂ </scp> and <scp> O ₂ </scp> at ambient conditions

Abstract Direct synthesis of hydrogen peroxide (DSHP) from H 2 and O 2 is indeed a promising sustainable alternative to the conventional anthraquinone oxidation process, yet achieving high H 2 O 2 productivity and selectivity simultaneously remains a significant challenge. Herein, we designed a diode‐inspired interfacial microenvironment to address this challenge by synchronizing the kinetic relay of the key transport and reaction steps in DSHP. Specifically, this microenvironment was fabricated by grafting hydrophobic silane molecules onto the carbon surface followed by loading palladium nanoparticles. Results indicate that the interfacial microenvironment enables an efficient relay of H 2 dissociation, H 2 O 2 formation and desorption, shutting down the reverse path of the side reaction. Benefiting from this diode‐inspired interfacial design, high H 2 O 2 productivity of 21,647.1 mol kg Pd −1 h −1 and H 2 O 2 selectivity of 93.3% were successfully achieved under ambient conditions. This work demonstrated the critical role of the interfacial microenvironment in regulating the synergy between mass transfer and reaction in heterogeneous reaction.