Carbon materials are considered promising 2/4 e⁻ oxygen reduction reaction (ORR) electrocatalysts for synthesizing H₂O₂/H₂O via regulating heteroatom dopants and functionalization. Here, various doped and functionalized graphene quantum dots (GQDs) are designed to reveal the crucial active sites of carbon materials for ORR to produce H₂O₂. Density functional theory (DFT) calculations predict that the edge structure involving edge N, B dopant pairs and further OH functionalization to the B (NBOH) is an active center for 2e⁻ ORR. To verify the above predication, GQDs with an enriched density of NBOH (NBO‐GQDs) are designed and synthesized by the hydrothermal reaction of NH₂ edge‐functionalized GQDs with H₃BO₃ forming six‐member heterocycle containing the NBOH structure. When dispersed on conductive carbon substrates, the NBO‐GQDs show H₂O₂ selectivity of over 90% at 0.7 –0.8 V versus reversible hydrogen electrode in the alkaline solution in a rotating ring‐disk electrode setup. The selectivity retains 90% of the initial value after 12 h stability test. In a flow cell setup, the H₂O₂ production rate is up to 709 mmol g_catalyst⁻¹ h⁻¹, superior to most reported carbon‐ and metal‐based electrocatalysts. This work provides molecular insight into the design and formulation of highly efficient carbon‐based catalysts for sustainable H₂O₂ production.

Carbon nanomaterials show outstanding promise as electrocatalysts for hydrogen peroxide (H₂O₂) synthesis via the two-electron oxygen reduction reaction. However, carbon-based electrocatalysts that are capable of generating H₂O₂ at industrial-level current densities (>300 mA cm⁻²) with high selectivity and long-term stability remain to be discovered. Herein, few-layer boron nanosheets are in-situ introduced into a porous carbon matrix, creating a metal-free electrocatalyst (B_n-C) with H₂O₂ production rates of industrial relevance in neutral or alkaline media. B_n-C maintained > 95% Faradaic efficiency during a 140-hour test at 300 mA cm⁻² and 0.1 V vs. RHE, and delivered a mass activity of 25.1 mol g_catalyst⁻¹ h⁻¹ in 1.0 M Na₂SO₄ using a flow cell. Theoretical simulations and experimental studies demonstrate that the superior catalytic performance originates from B atoms with adsorbed O atoms in the boron nanosheets. B_n-C outperforms all metal-based and metal-free carbon catalysts reported to date for H₂O₂ synthesis at industrial-level current densities.

Natural biomass-derived carbon material is one promising alternative to traditional graphene-based catalyst for oxygen electrocatalysis. However, their electrocatalytic performance were constrained by the limited modulating strategy. Herein, using N-doped commercial coconut shell-derived activated carbon (AC) as catalyst model, the controllably enhanced sp ²-C domains, through an flash Joule heating process, effectively improve the edge defect density and overall graphitization degree of AC catalyst, which tunes the electronic structure of N configurations and accelerates electron transfer, leading to excellent oxygen reduction reaction performance (half-wave potential of 0.884 V_RHE, equivalent to commercial 20% Pt/C, with a higher kinetic current density of 5.88 mA cm⁻²) and oxygen evolution reaction activity (overpotential of 295 mV at 10 mA cm²). In a Zn-air battery, the catalyst shows outstanding cycle stability (over 1200 h) and a peak power density of 121 mW cm⁻², surpassing commercial Pt/C and RuO₂ catalysts. Density functional theory simulation reveals that the enhanced catalytic activity arises from the axial regulation of local sp ²-C domains. This work establishes a robust strategy for sp ²-C domain modulation, offering broad applicability in natural biomass-based carbon catalysts for electrocatalysis.