Two-electron Oxygen Reduction Reaction Research Articles

Electrocatalysts for the Formation of Hydrogen Peroxide by Oxygen Reduction Reaction.

Hydrogen peroxide (H2O2) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H2O2 by two-electron oxygen reduction reaction (2e- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H2O2. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H2O2 by 2e- ORR. Finally, the advantages and novelty of 2e- ORR compared with traditional methods for H2O2 production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H2O2 production by 2e- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H2O2 and developing green chemical production.

Modulating Core Polarity in Metal-free Covalent Organic Frameworks for Selective Electrocatalytic Hydrogen Peroxide Production.

Tuning the charge density at the active site to balance the adsorption ability and reactivity of oxygen is extremely significant for driving a two-electron oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2). Herein, we have highlighted the influence of intermolecular polarity in covalent organic frameworks (COFs) on the efficiency and selectivity of electrochemical H2O2 production. Different C3 symmetric building blocks have been utilized to regulate the charge density at the active sites. The benzene-cored COF, which exhibits reduced polarity than the triazine-cored COF, displayed enhanced performance in H2O2 production, achieving 93.1% selectivity for H₂O₂ at 0.4 V with almost two-electron transfer and a faradaic efficiency of 90.5%. In-situ electrochemical Raman spectroscopy and scanning electrochemical microscopy (SECM) were employed to confirm H₂O₂ generation and analyze spatial reactivity patterns. These techniques provided detailed insights into localized catalytic behavior, emphasizing the influence of core polarity.

Boosting the O2-to-H2O2 Selectivity Using Sn-Doped Carbon Electrocatalysts: Towards Highly Efficient Cathodes for Actual Water Decontamination.

The high cost and often complex synthesis procedure of new highly selective electrocatalysts (particularly those based on noble metals) for H2O2 production are daunting obstacles to penetration of this technology into the wastewater treatment market. In this work, a simple direct thermal method has been employed to synthesize Sn-doped carbon electrocatalysts, which showed an electron transfer number of 2.04 and outstanding two-electron oxygen reduction reaction (ORR) selectivity of up to 98.0 %. Physicochemical characterization revealed that this material contains 1.53 % pyrrolic nitrogen, which is beneficial for the production of H2O2, and -C≡N functional group, which is advantageous for H+ transport. Moreover, the high volume ratio of mesopores to micropores is known to favor the quick escape of H2O2 from the electrode surface, thus minimizing its further oxidation. A purpose-made gas-diffusion electrode (GDE) was prepared, yielding 20.4 mM H2O2 under optimal electrolysis conditions. The drug diphenhydramine was selected for the first time as model organic pollutant to evaluate the performance of an electrochemical advanced oxidation process. In conventional electro-Fenton process (pH 3), complete degradation was achieved in only 15 min at 10 mA cm-2, whereas at natural pH 5.9 and 33.3 mA cm-2, almost overall drug removal was reached in 120 min.

Nature-inspired N, O Co-Coordinated Manganese Single-Atom Catalyst for Efficient Hydrogen Peroxide Electrosynthesis.

The two-electron oxygen reduction reaction (2e- ORR) is a pivotal pathway for the distributed production of hydrogen peroxide (H2O2). In nature, enzymes containing manganese (Mn) centers can convert reactive oxygen species into H2O2. However, Mn-based heterogeneous catalysts for 2e- ORR are scarcely reported. Herein, we developed a nature-inspired single-atom electrocatalyst comprising N, O co-coordinated Mn sites, utilizing carbon dots as the modulation platform (Mn CD/C). As-synthesized Mn CD/C exhibited exceptional 2e- ORR activity with an onset potential of 0.786 V and a maximum H2O2 selectivity of 95.8%. Impressively, Mn CD/C continuously produced 0.1 M H2O2 solution at 200 mA/cm2 for 50 h in the flow cell, with negligible loss in activity and H2O2 faradaic efficiency, demonstrating practical application potential. The enhanced activity was attributed to the incorporation of Mn atomic sites into the carbon dots. Theoretical calculations revealed that the N, O co-coordinated structure, combined with abundant oxygen-containing functional groups on the carbon dots, optimized the binding strength of intermediate *OOH at the Mn sites to the apex of the catalytic activity volcano. This work illustrates that carbon dots can serve as a versatile platform for modulating the microenvironment of single-atom catalysts and for the rational design of nature-inspired catalysts.

Selective O2-to-H2O2 Electrosynthesis by a High-Performance, Single-Pass Electrofiltration System Using Ibuprofen-Laden CNT Membranes.

Producing H2O2 through a selective, two-electron (2e) oxygen reduction reaction (ORR) is challenging, especially when it serves as an advanced oxidation process (AOP) for cost-effective water decontamination. Herein, we attain a 2e-selectivity H2O2 production using a carbon nanotube electrified membrane with ibuprofen (IBU) molecules laden (IBU@CNT-EM) in an ultrafast, single-pass electrofiltration process. The IBU@CNT-EM can generate H2O2 at a rate of 25.62 mol gCNT-1 h-1 L-1 in the permeate with a residence time of 1.81 s. We demonstrated that an interwoven, hydrophilic-hydrophobic membrane nanostructure offers an excellent air-to-water transport platform for ORR acceleration. The electron transfer number of the ORR for IBU@CNT at neutral pH was confirmed as 2.71, elucidating a near-2e selectivity to H2O2. Density functional theory (DFT) studies validated an exceptional charge distribution of the IBU@CNT for the O2 adsorption. The adsorption energies of the O2 and *OOH intermediates are proportional to the H2O2 selectivity (64.39%), higher than that of the CNT (37.81%). With the simple and durable production of H2O2 by IBU@CNT-EM electrofiltration, the permeate can actuate Fenton oxidation to efficiently decompose emerging pollutants and inactivate bacteria. Our study introduces a new paradigm for developing high-performance H2O2-production membranes for water treatment by reusing environmental functional materials.

Designing 1-nm-Thick MOF Nanosheets with Donor-Acceptor Complexes for Photosynthesis of H2O2 Using Water and Dioxygen Only.

Artificial photosynthesis of hydrogen peroxide (H2O2) presents a promising environmentally friendly alternative to the industrial anthraquinone process. This work designed ultrathin metal-organic framework (MOF) nanosheets on which porphyrin ligand as an electron donor (D) and anthraquinone (AQ) as an electron acceptor (A) are integrated as the D-A complexes. The porphyrin component allows the MOF nanosheets to absorb full-spectrum solar light while the acceptor AQ motif promotes central aluminum ion coordination, hindering layer stacking to achieve a thickness of 1.0 nm. The ultrathin D-A design facilitates the separation of electrons from the MOF skeleton to the AQ motif, which induces the direct two-electron oxygen reduction reaction (ORR) mediated by the reversible redox couple of AQ-AQH2 and multielectron water oxidation reaction (WOR) driven by holes remaining on the porphyrin part. In O2-saturated water, the ultrathin MOF nanosheets outperformed the AQ-free bulk and multilayered counterparts by 2.9 and 2.6 times in H2O2 production, respectively, achieving the apparent quantum yield of 4.8% at 420 nm. It also surpasses other benchmark photocatalysts, including the typical MOF photocatalyst, MIL-125-NH2, and organic polymeric photocatalysts. The ultrathin D-A MOF photocatalyst generated H2O2 via both two-electron ORR as a major path and two-electron WOR as a minor path. This approach presents a promising strategy for the rational design of efficient nanostructured photocatalysts for solar fuels and chemicals.

High density cobalt single atom catalysts for H2O2 electrosynthesis: A critical design of carbon nitride skeleton

Direct hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction (ORR) provides aburgeoning alternative to the industrial anthraquinone process.In this work, based on first-principles calculations and a targeted structural search, we predicted a new two-dimensional (2D) carbon nitride monolayer, PH-CN, accompanied by high mechanical stability and adequate intrinsic pyrrolic N-rich network, such remarkable merits ensure its greatpotential as substrates. Herein, we demonstrate how the coordination environment regulates the electronic structure of the Co central atom and thus steers the ORR selectivity and activity using a series of control samples based on the most prevalent CoN4 moiety. As expected, the acquired P-CoN4 and PH-CoN4 show excellent H2O2electrosynthesis performance with low thermodynamic overpotential of 0.02 and 0.07 V, as well as extremely high Co loadings of 26.28 and 27.42 wt%, respectively. This work sheds light on how the carbon nitride skeleton affects catalytic activities on Co-N-C catalysts.

Construction of One-Dimensional Covalent-Organic Framework Coordinated with Main Group Metals for Selective Electrochemical Synthesis of H2O2.

Covalent-organic frameworks (COFs) are promising electrocatalysts for the selective synthesis of H2O2 through the two-electron oxygen reduction reaction (2e- ORR). However, the design and synthesis of efficient and stable COF-based electrocatalysts is still challenging. In this work, a predesigned 1,10-phenanthroline-based one-dimensional COF (PYTA-PTDE-COF) was constructed to anchor main group metal (In, Sn, and Sb) as electrocatalysts toward 2e- ORR. The catalysts are featured with fully exposed metalated side chains. Structural characterization revealed that PYTA-PTDE-M's (M = In, Sn, and Sb) are all quite similar, except for the coordinated metal ions with the maintenance of good crystallinity. They all exhibited satisfying activity and selectivity toward 2e- ORR under alkaline conditions. Among them, PYTA-PTDE-Sb exhibited the best performance (Eonset is 0.765 V, the H2O2 selectivity is 96%, and the yield rate is 209.2 mmol gcat-1 h-1). Moreover, it also delivered superior stability with almost no attenuation of current density during the long-time test. Theoretical calculations revealed that the Sb metal site in the COFs has the lowest adsorption strength of *OOH, which could be the main reason for its superior selectivity. The PYTA-PTDE-Sb assembled zinc-air battery realizes not only the supply of clean energy but also the production of green chemicals, showing it is highly promising in practical applications. This work offers an example for designing main group metal-coordinated 1D COFs and reveals fundamental structure-activity relationship toward 2e- ORR.

A Computation-Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-Dimensional Conductive Metal-Organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

Grain boundary engineering for efficient and durable electrocatalysis

Grain boundaries in noble metal catalysts have been identified as critical sites for enhancing catalytic activity in electrochemical reactions such as the oxygen reduction reaction. However, conventional methods to modify grain boundary density often alter particle size, shape, and morphology, obscuring the specific role of grain boundaries in catalytic performance. This study addresses these challenges by employing gold nanoparticle assemblies to control grain boundary density through the manipulation of nanoparticle collision frequency during synthesis. We demonstrate a direct correlation between increased grain boundary density and enhanced two-electron oxygen reduction reaction activity, achieving a significant improvement in both specific and mass activity. Additionally, the gold nanoparticle assemblies with high grain boundary density exhibit remarkable electrochemical stability, attributed to boron segregation at the grain boundaries, which prevents structural degradation. This work provides a promising strategy for optimizing the activity, selectivity, and stability of noble metal catalysts through precise grain boundary engineering.

Magnetic field-enhanced two-electron oxygen reduction reaction using CeMnCo nanoparticles supported on different carbonaceous matrices

The current study illustrates the successful synthesis of Ce1.0Mn0.9Co0.1 nanoparticles, characterized through XRD, EPR, magnetization curves, and TEM/HRTEM/EDX analyses. These nanoparticles were then loaded into the carbon Vulcan XC72 and the carbon Printex L6 matrices in varying amounts (1, 3, 5, and 10 % w/w) via wet impregnation method to fabricate electrocatalysts for the 2-electron ORR. Before experimentation, the material was characterized via XPS and contact angle measurements. The electrochemical results produced significant findings, indicating that the electrocatalysts with the nanostructures modifying both carbon blacks notably augmented currents in rotating ring-disk electrode measurements, signifying enhanced selectivity for H2O2 production. Moreover, our research underscored the significant impact of Magnetic Field-Enhanced Electrochemistry, employing a constant magnetic field strength of 2000 Oe, on 2-electron ORR experiments. Particularly noteworthy were the observed results surpassing the ones without the magnetic field, demonstrating heightened currents and improved selectivity for H2O2 production (more than 90 %) facilitated by CeMnCo nanoparticles. These significant findings in electrocatalytic efficiency have practical implications, suggesting the potential for developing more efficient and selective catalysts for the 2-electron ORR.

Electrochemical production of HO2- and O2 for sulfide removal from sewage

In this study, a comparative analysis of two electrochemical methods for sulfide control in sewer networks was performed for the first time. In addition, the mechanism of sulfide control by HO2- was elucidated, and an analysis of the device operation and electrolyte selection was performed. The two-electron oxygen reduction reaction (2e--ORR) using untreated gas diffusion electrode (GDE) was superior to the hydrogen evolution reaction (HER) using stainless-steel mesh in terms of cell voltage, product formation, and sulfide suppression. The GDE maintained a stable HO₂⁻ production capacity, achieving a concentration of 4566.6 ± 173.3 mg L⁻¹ with a current efficiency (CE) of 84.13 ± 3.5 %. During the electrolysis period, a stable dissolved oxygen (DO) level in sewage was consistently observed due to continuous in-situ oxygen production in anode. HO2- exhibited a notable increase in sewage pH (10.20 ± 0.01), effectively inhibiting the release of 99.93 % of sulfides. Moreover, the combined treatment of HO2- and DO significantly surpassed that of individual treatments. Seawater treated with cation exchange resin (CER) emerged as the most promising alternative to freshwater as the electrolyte. Overall, this study demonstrates that in-situ generation of HO₂⁻ and oxygen is a more effective strategy for sulfide control in sewer systems.

Piezo-catalysis Mechanism Elucidation by Tracking Oxygen Reduction to Hydrogen Peroxide with In-situ EPR Spectroscopy.

For piezoelectric catalysis, the catalytic mechanism is a topic of great controversy, with debates centered around whether it belongs to the energy band theory of photocatalysis or the screening charge effect of electrochemical catalysis. Due to the formation of different intermediate active-species during two-electron oxygen reduction reaction (ORR) via electro- and photo-catalysis, the key to solving this problem is precisely monitoring the active species involved in ORR during electro-, photo-, and piezo-catalysis under identical condition. Here, a semiconductor material, BiOBr with abundant oxygen vacancies (BOB-OV) was found remarkable catalytic activity in H2O2 production by all three catalytic methods. By employing in-situ electron paramagnetic resonance (EPR) spectroscopy, the H2O2 evolution pathway through piezo-catalysis over BOB-OV was monitored, which showed a similar reaction pathway to that observed in photo-catalytic process. This finding represents solid evidence supporting the notion that piezo-catalytic mechanism of ORR is more inclined towards photo-catalysis rather than electro-catalysis. Significantly, this exploratory conclusion provides insight to deepen our understanding of piezo-catalysis.

Unveiling O2 adsorption on non-metallic active site for selective photocatalytic H2O2 production

Photocatalytic oxygen reduction reaction (ORR) offers a promising pathway for sustainable hydrogen peroxide (H2O2) production but faces challenges in developing catalysts with good ORR selectivity. Herein, we report that tailoring O2 adsorption on non-metallic active sites can optimize ORR selectivity. This concept is demonstrated on three carbon nitrides with different atomic configurations: polymeric carbon nitride (PCN), lithium-poly triazine imide (Li-PTI), and sodium-poly heptazine imide (Na-PHI). Na-PHI emerges as a strong candidate for H2O2 production due to the end-on adsorption mode and suitable adsorption strength with O2. Synthesized Na-PHI, PCN, and Li-PTI are characterized, with Na-PHI showing superior light absorption, charge carrier separation, and remarkable selectivity (92 %) for two-electron ORR. Consequently, Na-PHI achieves a high H2O2 generation rate of 3.48 mmol g−1 h−1, surpassing Li-PTI and PCN by 9.2 and 33 times, respectively. This study underscores the importance of O2 adsorption on non-metallic active sites for selective photocatalytic H2O2 generation.

Heterogeneous electro-Fenton oxidation of Congo red using carboxylic group activated carbon felt cathode: Electrokinetic mechanism and performance

In this study, the carboxyl functional group (–COOH) saturated-carbon-felt (ACF) as functional cathode was prepared and used in heterogenous (Fe2+) electro-Fenton (EF) catalytic degradation of Congo red (CR) in waster. As a heterogeneous catalyst, size-controlled magnetite (Fe3O4) nanoparticles (MNPs) were applied to the surface of the ACF cathode. The selectivity of ACF toward the two-electron oxygen-reduction reaction was estimated based on the proportion of H2O2 production; it was determined as >89 %. The removal efficiency of ACF for CR dye was 94 ± 2 % over 40 min reaction time, almost double that of a pristine CF cathode (48 ± 3 %). The kinetics data fitted to a pseudo-second order (PSO) model with K2 of 8.8 × 10−4 ± 1.72 × 10−5 mol−1 cm3 min−1 (0.88 ± 0.02 M−1 min−1). The mineralization current efficiency and TOC for CR were observed as 58 ± 2 %, and 83 ± 3 %, respectively. Overall, the results insight that the system could be a viable alternative method for treating dye-contaminated water.

Efficient H2O2 Synthesis through a Two-Electron Oxygen Reduction Reaction by Electrocatalysts.

The two-electron oxygen reduction reaction (2e-ORR) for the sustainable synthesis of hydrogen peroxide (H2O2) has demonstrated considerable potential for local production of this environmentally friendly chemical oxidant on small, medium, and large scales. This method offers a promising alternative to the energy-intensive anthraquinone approach, placing a primary emphasis on the development of efficient electrocatalysts. Improving the efficiency of electrocatalysts and uncovering their catalytic mechanisms are essential steps in achieving high 2e-ORR activity, selectivity, and stability. This comprehensive review summarizes recent advancements in electrocatalysts for in-situ H2O2 production, providing a detailed overview of the field. In particular, the review delves into the design, fabrication, and investigation of catalytic active sites contributing to H2O2 selectivity. Additionally, it highlights a range of electrocatalysts including pure metals and alloys, transition metal compounds, single-atom catalysts, and carbon-based catalysts for the 2e-ORR pathway. Finally, the review addresses significant challenges and opportunities for efficient H2O2 electrosynthesis, as well as potential future research directions.

Enhanced electron transfer kinetics via constructing co-catalytic system of cerium oxide and carbon dots enabling efficient electrosynthesis of hydrogen peroxide in neutral media

The sluggish kinetics coupled with the competition of four-electron pathway in neutral media diminishes the production efficiency of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e− ORR). To address this dilemma, this contribution proposes one electron modulation strategy to expedite the charge transfer capability by integrating carbon dots with CeO2 (CDs/CeO2) for the efficient neutral electrosynthesis of H2O2. It was found that the integration could effectively bolster both the activity and selectivity of 2e− ORR on CDs and CeO2. Remarkably, the highest 2e− selectivity could reach up to 92 % for the optimized CDs/CeO2, substantially surpassing that (77 %) of pristine CeO2, together with about 1.5 times enhancement of activity. Meanwhile, it also delivered a superior long durability at 20 mA cm−2 for 24 h and a high Faraday efficiency of 97 %. Further in-situ transient potential scanning (TPS) technique revealed that the pseudo-capacitance and charge storage capacity of CeO2 were significantly tuned by CDs during dynamic ORR process, being conducive to the reaction kinetics and the 2e− selectivity. The findings in this work not only extends the co-catalytic system based on CDs and rare earth materials for 2e− ORR, but also offers novel insights into correlation between their electron distribution dynamics and 2e− ORR performance.

Perfect Is Perfect: Nickel Prussian Blue Analogue as A High-Efficiency Electrocatalyst for Hydrogen Peroxide Production.

Prussian blue analogues (PBA) are a large family of functional materials with diverse applications such as in electrochemical fields. However, their use in the emerging two-electron oxygen reduction reaction for clean production of hydrogen peroxide (H2O2) is lagging. Herein, a general solvent exchange induced reconstruction strategy is demonstrated, through which an abnormal NiNi-PBA superstructure is synthesized as a high-performance electrocatalyst for H2O2 generation. The resultant NiNi-PBA superstructure has a stoichiometric composition with saturated lattice water, and a leaf-like morphology composed of interconnected small-size nanosheets with identical orientation and predominate {210} side surface exposure. Our studies show that the Ni-N centers on {210} facets are the active sites, and the saturated lattice H2O favors a six-coordinated environment that results in high selectivity. The "perfect" structure including stoichiometric composition and ideal facet exposure leads to a high selectivity of ~100% and H2O2 yield of 5.7 mol g-1 h-1, superior to the reported MOF-based electrocatalysts and most other electrocatalysts.

Synergistic effect of lightning rod and piezo-photocatalysis in sea urchin-shape Zn-MOF-74@g-C3N4 step-scheme heterojunction for H2O2 production under visible light irradiation

Piezo-photocatalytic H2O2 production was an emerging environmental technology that could convert solar energy into green chemicals, garnering significant attention. This study combined lightning rod effect and piezo-photocatalysis to achieve H2O2 production through an indirect two-electron oxygen reduction reaction pathway. A composite catalyst, sea urchin-shaped Zn-MOF-74@g-C3N4, had a surface of spherical Zn-MOF-74 made up of graphite phase carbon nitride nanoneedles with high curvature tips. These tips could induce a “lightning rod effect” property, accelerating charge transfer and separation by guiding electron migration along the sharp tip direction. The piezo-photocatalytic process, along with the construction of step-scheme heterojunction, generated a dual electric field, significantly enhancing the separation and migration rate of photogenerated carriers. As a result, the prepared Zn-MOF-74@g-C3N4 demonstrated a higher H2O2 production rate under the synergistic effect of lightning rod and piezo-photocatalysis. Free radical trapping experiments were conducted on various active species to uncover the mechanism behind the piezo-photocatalytic dual electric field coupling to produce H2O2.

First-principles study of electrochemical H2O2 production on Pd-B40 single-atom catalyst

Hydrogen peroxide (H2O2), a versatile green compound, is increasingly in demand. The electrochemical two-electron oxygen reduction reaction (2e− ORR) is a simple and environmentally friendly substitute method to the traditional anthraquinone oxidation method for H2O2 production. This study systematically investigates the 2e− ORR process on single transition metal atom-loaded boron fullerene (M − B40) using density functional theory calculations. In evaluating the stability of the catalysts, we found that Au, Pd, Pt, Rh, and Ir atoms adsorbed on hexagonal or heptagonal sites of B40 exhibit good stability. Among these, Pd-modified B40 heptagonal cavity (Pd-B40-heptagonal) demonstrates an ideal Gibbs free energy change for OOH* (4.49 eV) and efficiently catalyzes H2O2 production at a low overpotential (0.27 V). Electronic structure analysis reveals that electron transfer between Pd-B40-heptagonal and adsorbed O2 facilitates O2 activation. Additionally, the high 2e− ORR activity of Pd-B40-heptagonal is attributed to electron transfer from the Pd-d orbitals to the π* anti-bonding of p orbitals of OOH*, moderately activating the O-O bond. This study offers valuable understanding designing high-performance electrocatalysts for 2e− ORR.