Interfacial electronic transfer triggered dual-site synergistic catalysis on Fe3N/C for efficient H2O2 electro-synthesis

Developing efficient electrocatalysts for the two-electron oxygen reduction reaction (2e − ORR) is pivotal for the decentralized production of hydrogen peroxide. Herein, we present a high-performance catalyst composed of highly dispersed Fe 3 N nanoparticles anchored on hierarchical porous carbon nanosheets (Fe 3 N@HPC), derived from petroleum pitch. In situ infrared spectroscopy and density functional theory calculations demonstrate that the robust electronic interaction between Fe 3 N nanoparticles and heteroatom (N/O)-activated carbon atoms establishes dual active sites comprising both Fe 3 N and carbon atoms, while shifting the d-band center of Fe sites down to −1.18 eV. This electronic modulation effectively weakens the adsorption strength of the *OOH intermediate on Fe sites, thereby reducing the reaction energy barrier and promoting the 2e − pathway through suppressing O–O bond cleavage. Simultaneously, the Fe 3 N nanoparticles induce local charge redistribution, leading to the formation of positively charged carbon atoms, which collectively enhances both the selectivity and activity for H 2 O 2 production. Coupled with the enhanced mass transport from the hierarchical pores, the Fe 3 N@HPC catalyst exhibits exceptional performance. In a 0.1 M KOH H-cell, it achieves a remarkable H 2 O 2 production rate of 1621 mmol·g cat −1 h −1 with 87.7 % Faradaic efficiency (FE) at 0.5 V (vs. RHE). When configured in a flow cell with 1 M KOH, it maintains a high production rate of 2315 mmol·g cat −1 h −1 (79.5 % FE) at 0.5 V (vs. RHE) and demonstrates outstanding stability over 120 h of continuous operation at 0 V (vs. RHE), showing promising application potential for industrial H 2 O 2 electro-synthesis.