High Oxygen Reduction Reaction Activity Research Articles

ZIF-8 derived iron-, sulphur-, and nitrogen-doped catalysts for anion-exchange membrane fuel cell application

This study presents the preparation of tridoped Fe, N, S carbon-based catalysts using ZIF-8 as the main carbon source and iron(II)acetate, 1,10-phenanthroline, ammonia gas and thiourea as precursors for Fe, N and S elements. Thiourea was mixed via planetary ball-milling with a Fe–N–C catalyst prepared by inert gas pyrolysis, and different pyrolysis conditions were applied thereafter. The main goal of the work is to synthesise active non-precious metal electrocatalysts for oxygen reduction reaction (ORR). High electrocatalytic ORR activity in alkaline media was observed for the two materials obtained after thiourea addition and subsequent pyrolysis. Physico-chemical characterisation revealed successful S- and N-doping for all three catalysts with enhanced porosity for the two materials that were subjected to additional pyrolysis after the thiourea addition. The sulphur doping was highest for the FeNSC3 material that was subjected to a second pyrolysis in N2 and a third pyrolysis in NH3, compared to the FeNSC2 material that was subjected to a single pyrolysis in NH3 flow after thiourea addition. The ORR activity of FeNSC2 with half-wave potential of 0.88 V was slightly higher than that of FeNSC3, and the former was selected for evaluation as a cathode catalyst in an anion-exchange membrane fuel cell.

Monolayer Ta2Se: A low-cost catalyst with enhanced stability and high basal plane activity for oxygen reduction reaction

The search for cost-effective two-dimensional (2D) electrocatalysts is accelerating as these materials emerge as pivotal alternatives to traditional energy technologies for fuel cells. In this work, we report a low-cost, high-performance Ta2Se monolayer as an electrocatalyst for the oxygen reduction reaction (ORR) through first-principles calculations. The Ta2Se monolayer exhibits notable stability and low cleavage energy, underscoring its practical potential for experimental synthesis. Our computations show that the Ta2Se monolayer has a metallic band structure with substantial electronic states at the Fermi level, which suggests the favorable electron transport properties. Remarkably, the outer Ta atoms in the basal plane of Ta2Se monolayer are identified as ORR active sites, exhibiting a competitive selection for dissociative and associative four-electron pathways alongside outstanding catalytic activity. Through examining the surface coverage impacts on ORR, we disclose that at a moderate oxygen coverage, the Ta2Se monolayer's limiting potential reaches approximately 0.9 eV, outstripping the conventional Pt electrodes, thus confirming its superior ORR catalytic capability. The low cost, active basal plane sites, and high ORR activity make the Ta2Se monolayer a competitive candidate for advanced fuel cell components.

A highly oxygen reduction reaction active and CO2 durable high-entropy cathode for solid oxide fuel cells

One big obstacle for the oxygen reduction reaction (ORR) electrode in solid oxide fuel cells (SOFCs) is the poor reaction activity and fast degradations caused by CO2 poisoning. Here we report our design of an active A-site Ca-rich high-entropy Pr0.1875Ba0.1875Sr0.1875La0.1875Ca0.25CoO3-δ (PBSLC25C) electrode, guided by the O p-band theory. When applied as a cathode in solid oxide fuel cells (SOFCs), it demonstrates high ORR activity and excellent CO2 tolerance under realistic operating conditions. Ni-YSZ-based anode-supported cells with PBSLC25C cathodes demonstrate excellent peak power densities of 1.14 W cm−2, 1.04 W cm−2, and 0.77 W cm−2 in the air with 1%, 5%, and 10% CO2, respectively, at 750 °C. The engineered high-entropy PBSLC25C effectively diminishes the CO2 poisoning effect and maintains active surfaces for fast oxygen exchange, as confirmed by the cell durability test in air containing CO2 (5 and 10 vol%), Raman spectroscopy, and density functional theory calculations.

Well-dispersed Pt/Nb2O5 on zeolitic imidazolate framework derived nitrogen-doped carbon for efficient oxygen reduction reaction

In this work, an advanced hybrid material was constructed by incorporating niobium pentoxide (Nb2O5) nanocrystals with nitrogen-doped carbon (NC) derived from ZIF-8 dodecahedrons, serving as a support, referred to as Nb2O5/NC. Pt nanocrystals were dispersed onto Nb2O5/NC using a simple impregnation reduction method. The obtained Pt/Nb2O5/NC electrocatalyst showed high oxygen reduction reaction (ORR) activity due to three-phase mutual contacting structure with well-dispersed Pt and Nb2O5 NPs. In addition, the conductive NC benefits electron transfer, while the induced Nb2O5 can regulate the electronic structure of Pt element and anchor Pt nanocrystals, thereby enhancing the ORR activity and stability. The half-wave potential (E 1/2) for Pt/Nb2O5/NC is 0.886 V, which is higher than that of Pt/NC (E 1/2 = 0.826 V). The stability examinations demonstrated that Pt/Nb2O5/NC exhibited higher electrocatalytic durability than Pt/NC. Our work provides a new direction for synthesis and structural design of precious metal/oxides hybrid electrocatalysts.

Interlayer Polymerization to Construct a Fully Conjugated Covalent Organic Framework as a Metal-Free Oxygen Reduction Reaction Catalyst for Anion Exchange Membrane Fuel Cells.

Two-dimensional (2D) covalent organic frameworks (COFs) have a multilayer skeleton with a periodic π-conjugated molecular array, which can facilitate charge carrier transport within a COF layer. However, the lack of an effective charge carrier transmission pathway between 2D COF layers greatly limits their applications in electrocatalysis. Herein, by employing a side-chain polymerization strategy to form polythiophene along the nanochannels, a conjugated bridge is constructed between the COF layers. The as-synthesized fully conjugated COF (PTh-COF) exhibits high oxygen reduction reaction (ORR) activity with narrowed energy band gaps. Correspondingly, PTh-COF is tested as a metal-free cathode catalyst for anion exchange membrane fuel cells (AEMFCs) which showed a maximum power density of 176mWcm-2 under a current density of 533mAcm-2. The density functional theory (DFT) calculation reveals that interlayer conjugated polythiophene optimizes the electron cloud distribution, which therefore enhances the ORR performance. This work not only provides new insight into the construction of a fully conjugated covalent organic framework but also promotes the development of new metal-free ORR catalysts.

Novel electrocatalytic capacitive deionization with catalytic electrodes for selective phosphonate degradation: Performance and mechanism

Phosphonate is becoming a global interest and concern owing to its environment risk and potential value. Degradation of phosphonate into phosphate followed by the recovery is regarded as a promising strategy to control phosphonate pollution, relieve phosphorus crisis, and promote phosphorus cycle. Given these objectives, an anion-membrane-coated-electrode (A-MCE) doped with Fe-Co based carbon catalyst and cation-membrane-coated-electrode (C-MCE) doped with carbon-based catalyst were prepared as catalytic electrodes, and a novel electrocatalytic capacitive deionization (E-CDI) was developed. During charging process, phosphonate was enriched around A-MCE surface based on electrostatic attraction, ligand exchange, and hydrogen bond. Meanwhile, Fe2+ and Co2+ were self-oxidized into Fe3+ and Co3+, forming a complex with enriched phosphonate and enabling an intramolecular electron transfer process for phosphonate degradation. Additionally, benefiting from the stable dissolved oxygen and high oxygen reduction reaction activity of C-MCE, hydrogen peroxide accumulated in E-CDI (158 μM) and thus hydroxyl radicals (·OH) were generated by activation. E-CDI provided an ideal platform for the effective reaction between ·OH and phosphonate, avoiding the loss of ·OH and triggering selective degradation of most phosphonate. After charging for 70 min, approximately 89.9% of phosphonate was degraded into phosphate, and phosphate was subsequently adsorbed by A-MCE. Results also showed that phosphonate degradation was highly dependent on solution pH and voltage, and was insignificantly affected by electrolyte concentration. Compared to traditional advanced oxidation processes, E-CDI exhibited a higher degradation efficiency, lower cost, and less sensitive to co-existed ions in treating simulated wastewaters. Self-enhanced and selective degradation of phosphonate, and in-situ phosphate adsorption were simultaneously achieved for the first time by a E-CDI system, showing high promise in treating organic-containing saline wastewaters.

Self‐Sacrificial Template Synthesis of Fe‐N‐C Catalysts with Dense Active Sites Deposited on A Porous Carbon Network for High Performance in PEMFC

AbstractIron‐nitrogen‐carbon (Fe‐N‐C) single‐atom catalysts are promising sustainable alternatives to the costly and scarce platinum (Pt) to catalyze the oxygen reduction reactions (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). However, Fe‐N‐C cathodes for PEMFC are made thicker than Pt/C ones, in order to compensate for the lower intrinsic ORR activity and site density of Fe‐N‐C materials. The thick electrodes are bound with mass transport issues that limit their performance at high current densities, especially in H2/air PEMFCs. Practical Fe‐N‐C electrodes must combine high intrinsic ORR activity, high site density, and fast mass transport. Herein, it has achieved an improved combination of these properties with a Fe‐N‐C catalyst prepared via a two‐step synthesis approach, constructing first a porous zinc‐nitrogen‐carbon (Zn‐N‐C) substrate, followed by transmetallating Zn by Fe via chemical vapor deposition. A cathode comprising this Fe‐N‐C catalyst has exhibited a maximum power density of 0.53 W cm−2 in H2/air PEMFC at 80 °C. The improved power density is associated with the hierarchical porosity of the Zn‐N‐C substrate of this work, which is achieved by epitaxial growth of ZIF‐8 onto g‐C3N4, leading to a micro‐mesoporous substrate.

Regulating the Electronic Synergy of Asymmetric Atomic Fe Sites with Adjacent Defects for Boosting Activity and Durability toward Oxygen Reduction

AbstractThe oxygen reduction reaction (ORR) plays a fundamental role in sustainable energy technologies. However, the creation of non‐precious metal electrocatalysts with high ORR activity and durability under all pH conditions is of great significance but remains challenging. Herein, the aim is to overcome this challenge by creating a Fe single atom catalyst on a 2D defect‐containing nitrogen‐doped carbon support (Fe1/DNC) via a microenvironment engineering strategy. Microkinetic modeling reveals that FeN4(OH) moieties are the real active sites under reaction conditions. Due to the synergistic promotion effect of denser accessible FeN4(OH) moieties and defect‐induced electronic properties, Fe1/DNC catalyst achieves extraordinary ORR activity under alkaline, acidic, and neutral conditions, with half‐wave potentials of 0.95, 0.82, and 0.70 V, respectively. Moreover, a negligible performance decay is observed with this Fe catalyst in stability and methanol tolerance tests. Zn‐air battery employing Fe1/DNC delivers remarkable peak power density and long‐term operational durability. Theoretical analysis provides compelling evidence that the defects adjacent to FeN4(OH) moieties can endow an inductive effect to reshape electronic properties to balance the OOH* formation and OH* reduction. This work offers insight into the regulation of asymmetric coordination structure and electronic properties of metal sites for boosting electrocatalytic activity and stability.

Optimization and regulation of catalytic activity and stability: Pt–Ni diamond-shaped pearl nanochains with core-shell structure as high-efficient oxygen reduction reaction catalysts

The low utilization efficiency and poor stability of carbon-supported Pt nanoparticles (Pt/C) catalyst are two main problems of proton exchange membrane fuel cells (PEMFC), which can improve the catalytic performance by forming alloys and precisely regulating morphology and structures. Here, we introduced a simple and direct method for synthesizing Pt–Ni diamond-shaped pearl nanochains (Pt–Ni DP-NCs) as efficient electrocatalyst for oxygen reduction reaction (ORR). The alloying with Ni could enhance the catalytic activity, but because of leaching out of Ni during the cathodic reaction process, which causes a poor stability. To achieve the optimal point for both high activity and robust stability, a portion of Ni is selectively etched from Pt–Ni DP-NCs precursor in advance. During the process of de-alloying, Pt atoms with high catalytic activity are exposed to the surface of the nanochain after atomic rearrangement, thus obtaining Pt–Ni etched diamond-shaped pearl nanochains (Pt–Ni EDP-NCs) with 1D core-shell structure, which consisted of Pt–Ni as the core and Pt as the shell. Benefitting from the unique 1D core-shell structure and composition, Pt–Ni EDP-NCs-9 (etched for 9 h) exhibits high catalytic activity and robust stability for ORR. The mass activity of the sample Pt–Ni EDP-NCs-9 is 0.43 A/mgPt, which is 1.65 times higher than that of the Pt–Ni DP-NCs (0.26 A/mgPt), and 2.05 times higher than that of commercial Pt/C (0.21 A/mgPt). In addition, the 1D core-shell structure enables Pt–Ni EDP-NCs to be highly stable, which only lost by 8.6% of mass activity after 10,000 long cycles, whereas Pt–Ni DP-NCs suffers from a 34% loss under the same conditions. This work provides a strategic approach for designing efficient Pt-based catalysts that simultaneously modulate activity and stability.

Self-powered Pb(II) removal driven by Zn-air batteries using N, P-doped active straw carbon as cathode

Electrochemical systems have been widely applied in heavy-metal ions (HMIs) pollution control, while their applications are greatly restricted by excessive energy consumption. Self-powered environmental remediation systems (SERSs) can shed the energy reliance to achieve HMIs decontamination and simultaneous electricity output through electrokinetic migration. In this work, SERSs based on Zn-air batteries (ZABs) were achieved to remove bivalent lead (Pb(II)) by circulating effluent as electrolyte. Straw biomass derived N, P functional active nanocarbon (NP-ASC) with hierarchical porosity and electron modulation effect was designed for achieving high oxygen reduction reaction (ORR) activity and efficient Pb(II) uptake. SERSs with electrode active area of 1 cm2 realize outstanding Pb(II) removal efficiency (98.1 %) and electricity generation (67.5 mWh∙cm−2) in simulated sewage. ZABs assembled with NP-ASC delivered specific capacity of 795 mAh∙g−1 and cycling stability for 340 h. This study provides a guide for designing a novel SERS using functionalized biomass nanocarbon.

TiN as Radical Scavenger in Fe─N─C Aerogel Oxygen Reduction Catalyst for Durable Fuel Cell.

Fe─N─C is the most promising alternative to platinum-based catalysts to lower the cost of proton-exchange-membrane fuel cell (PEMFC). However, the deficient durability of Fe─N─C has hindered their application. Herein, a TiN-doped Fe─N─C (Fe─N─C/TiN) is elaborately synthesized via the sol-gel method for the oxygen-reduction reaction (ORR) in PEMFC. The interpenetrating network composed by Fe─N─C and TiN can simultaneously eliminate the free radical intermediates while maintaining the high ORR activity. As a result, the H2 O2 yields of Fe─N─C/TiN are suppressed below 4%, ≈4 times lower than the Fe─N─C, and the half-wave potential only lost 15mV after 30 kilo-cycle accelerated durability test (ADT). In a H2 ─O2 fuel cell assembled with Fe─N─C/TiN, it presents 980mAcm-2 current density at 0.6V, 880mWcm-2 peak power density, and only 17mV voltage loss at 0.80Acm-2 after 10 kilo-cycle ADT. The experiment and calculation results prove that the TiN has a strong adsorption interaction for the free radical intermediates (such as *OH, *OOH, etc.), and the radicals are scavenged subsequently. The rational integration of Fe single-atom, TiN radical scavenger, and highly porous network adequately utilize the intrinsic advantages of composite structure, enabling a durable and active Pt-metal-free catalyst for PEMFC.

Carbon materials co-doped with nitrogen and sulfur for highly efficient catalytic activity in oxygen reduction and evolution

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) represent crucial steps in the functioning of fuel cells and metal-air batteries. Designing bifunctional oxygen electrode catalysts with high activity for both ORR and OER remains an immense challenge. In this study, we address this challenge by employing in-situ polymerization to design nitrogen and sulfur co-doped carbon materials (NSCs). The resulting NSC-1000–3 exhibits an onset potential of 1.03 V vs. RHE and a half-wave potential (E1/2) of approximately 0.89 V during ORR in an alkaline solution. When compared to commercial Pt/C, it demonstrates a positive shift of 60 mV in the half-wave potential. Furthermore, NSC-1000–3 displays outstanding oxygen evolution performance. At a current density of 10 mA cm−2, its performance matches that of RuO2. This material demonstrates exceptional performance in both ORR and OER, showcasing the synergistic doping effects of nitrogen and sulfur.

General Pyrolysis for High-Loading Transition Metal Single Atoms on 2D-Nitro-Oxygeneous Carbon as Efficient ORR Electrocatalysts.

Single-atom catalysts (SACs) possess the potential to involve the merits of both homogeneous and heterogeneous catalysts altogether and thus have gained considerable attention. However, the large-scale synthesis of SACs with rich isolate-metal sites by simple and low-cost strategies has remained challenging. In this work, we report a facile one-step pyrolysis that automatically produces SACs with high metal loading (5.2-15.9 wt %) supported on two-dimensional nitro-oxygenated carbon (M1-2D-NOC) without using any solvents and sacrificial templates. The method is also generic to various transition metals and can be scaled up to several grams based on the capacity of the containers and furnaces. The high density of active sites with N/O coordination geometry endows them with impressive catalytic activities and stability, as demonstrated in the oxygen reduction reaction (ORR). For example, Fe1-2D-NOC exhibits an onset potential of 0.985 V vs RHE, a half-wave potential of 0.826 V, and a Tafel slope of -40.860 mV/dec. Combining the theoretical and experimental studies, the high ORR activity could be attributed its unique FeO-N3O structure, which facilitates effective charge transfer between the surface and the intermediates along the reaction, and uniform dispersion of this active site on thin 2D nanocarbon supports that maximize the exposure to the reactants.

Efficient preparation of carbon materials composed of warped graphene layers via in-situ nano-templating and estimation of oxygen reduction reaction activity

The warped graphene layer (WGL) has garnered attention as a potential alternative to Pt for oxygen reduction reaction (ORR) catalysts and as a platform for enhancing the activity of Pt or molecular catalysts through interactions. We propose an in-situ nano-templating method for the preparation and mass production of WGLs and demonstrate its efficiency. The in-situ nano-templating method facilitates the synthesis of materials with three-dimensional curvature by concurrently generating nanoparticles and carbonizing. The synthesized WGLs exhibited high ORR activity in acidic conditions. Although the ORR activity was not correlated with the surface area, it was strongly correlated with the curvature radius of the WGLs. This activity was considered to arise owing to the optimization of oxygen adsorption ΔG0 with the decrease in the curvature radius of the WGLs; furthermore, the physicochemical characteristics of WGL possesses continuity of carbon layers and exhibit a Fermi level higher than the O2/H2O reduction potential. This report elucidates experimentally that WGLs contribute to ORR activity, suggesting the importance of incorporating WGLs in the development of non-precious metal catalysts.

Electrocatalytic degradation of Favipiravir by heteroatom (P and S) doped biomass-derived carbon with high oxygen reduction reaction activity

In this study, a biomass-derived carbon block with heteroatoms (P and S) self-doped graphene structure was successfully synthesized by spent coffee grounds (SCG) directly sintered method. The spent coffee grounds biomass-derived carbon (SCC) block was used as electrocatalytic electrode to effectively degrade the antiviral drug of Favipiravir (FAV) in water, which represented excellent oxygen reduction reaction (ORR) activity with the H2O2 production. The doped heteroatoms in the graphene structure of SCC provided many active sites in the electrocatalytic electrode for ORR as well as more production of reactive OH･. Based on the structural characterization, radical species identification and intermediate products analysis, the reaction mechanism of FAV degradation by the SCC block electrode was proposed. This catalytic system also showed high ecological safety that the ecological toxicity for Vibrio fischeri was significantly reduced with the degradation process of FAV. The degradation of FAV in recycle test and in real sample of lake water, well water, tap water all demonstrated high stability of structure and catalytic activity of SCC. The electrocatalytic system based on SCC block electrode has realized the recycling and utilization of biomass resources and has promising application on the removal of environmental pollutants.

N‐Decorated Main‐Group MgAl2O4 Spinel: Unlocking Exceptional Oxygen Reduction Activity for Zn‐Air Batteries

AbstractThe development of economical and efficient oxygen reduction reaction (ORR) catalysts is crucial to accelerate the widespread application rhythm of aqueous rechargeable zinc‐air batteries (ZABs). Here, a strategy is reported that the modification of the binding energy for reaction intermediates by the axial N‐group converts the inactive spinel MgAl2O4 into the active motif of MgAl2O4‐N. It is found that the introduction of N species can effectively optimize the electronic configuration of MgAl2O4, thereby significantly reducing the adsorption strength of *OH and boosting the reaction process. This main‐group MgAl2O4‐N catalyst exhibits a high ORR activity in a broad pH range from acidic and alkaline environments. The aqueous ZABs assembled with MgAl2O4‐N shows a peak power density of 158.5 mW cm−2, the long‐term cyclability over 2000 h and the high stability in the temperature range from ‐10 to 50 °C, outperforming the commercial Pt/C in terms of activity and stability. This work not only serves as a significant candidate for the robust ORR electrocatalysts of aqueous ZABs, but also paves a new route for the effective reutilization of waste Mg alloys.

Electrochemically assisted polymerization synthesis of ZIF-derived Fe-N/C with high oxygen reduction reaction activity

Abstract The zeolitic imidazolate framework-8 (ZIF-8)-derived Fe-N/C catalysts show excellent oxygen reduction reactions (ORR) performance, but the harsh synthesis conditions and low yields have greatly limited their commercialization. Herein, we report an electrochemical-assisted polymerization method to produce a Fe-N/C structure (EC-Fe-N/C) with a high surface area (954.583 m2 g−1), high dispersion of Fe (2.2 wt %), and abundant N (2.05 wt %). The hierarchical structure exhibits excellent ORR activity (half-wave potential 0.88 V, in alkaline media) and outstanding zinc-air battery performance (energy density 821.3 mAh g−1 Zn, specific capacity 1017.1 Wh kg−1 Zn). This work may provide a simple and effective strategy to rationally design the Fe-N/C porous structure for highly efficient ORR activity.

Highly Active and Stable Bimetallic Ordered Catalysts for Oxygen Reduction Reaction Improvement in Polymer Exchange Membrane Fuel Cells

Demand for replacing the Pt catalyst in proton exchange membrane fuel cells (PEMFCs) has increased because Pt metal is rare and high cost. The most reasonable way is synthesizing Pt-base alloy using transition metals such as Co, Ni, Fe, and Mo. The Pt-based alloy catalysts exhibit excellent catalytic activity by creating a synergistic effect through the interaction between Pt and the transition metals. Here we present the best PtNi alloy composition and maximize the performance of the oxygen reduction reaction (ORR) activity in fuel cells by annealing the alloy under a hydrogen atmosphere. The Pt7Ni3/C catalyst indicated a higher ORR activity than other compositions due to different structural changes, and the annealing catalysts at 700 °C under an H2 atmosphere improved the electrochemical activity and stability. The heat treatment increased the conductivity by reducing oxygen bonding as well as changing the structure into an ordered face-centered tetragonal (FCT) structure with good activity. The result of these studies provides a new way to develop high-performance and low-cost catalyst materials for fuel cells.

Precise Engineering of the Electrocatalytic Activity of FeN4-Embedded Graphene on Oxygen Electrode Reactions by Attaching Electrides.

Using first-principles calculations combined with a constant-potential implicit solvent model, we comprehensively studied the activity of oxygen electrode reactions catalyzed by electride-supported FeN4-embedded graphene (FeN4Cx). The physical quantities in FeN4Cx/electrides, i.e., work function of electrides, interlayer spacing, stability of heterostructures, charge transferred to Fe, d-band center of Fe, and adsorption free energy of O, are highly intercorrelated, resulting in activity being fully expressed by the nature of the electrides themselves, thereby achieving a precise modulation in activity by selecting different electrides. Strikingly, the FeN4PDCx/Ca2N and FeN4PDCx/Y2C systems maintain a high oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) activity with the overpotential less than 0.46 and 0.62 V in a wide pH range. This work provides an effective strategy for the rational design of efficient bifunctional catalysts as well as a model system with a simple activity-descriptor, helping to realize significant advances in energy devices.

Enriched Ti3+ in TiONC electrocatalyst for efficient H2O2 generation via 2-electron oxygen reduction reaction

The 2-electron electrochemical oxygen reduction reaction (ORR) is considered a viable method for synthesizing H2O2 because of its efficiency and environmental friendliness. However, conventional catalysts for this reaction predominantly rely on high-cost metals and require complex preparation procedures. Herein, we synthesized an electrocatalyst containing TiN and N-doped carbon via the pyrolysis of melamine and MIL125(Ti)–NH2. The effects of melamine and pyrolysis temperature on the chemical composition and defect site formation were investigated. Importantly, the obtained results suggest that the generated Ti3+ sites are more important in enhancing the performance of the 2-electron ORR, surpassing defective carbon and oxygen functional groups. In particular, the resulting TiONC-MA-1000 catalyst prepared through pyrolysis at 1,000 °C contained abundant Ti3+ sites, resulting in high 2-electron ORR activity with a molar selectivity exceeding 91 % and high stability over a 12 h testing period. The electrochemical H2O2 generation experiments conducted in an H-cell configuration employing TiONC-MA-1000 as the electrocatalyst yielded 6.99 mol⋅gcatalyst−1⋅h−1 H2O2. Therefore, the present study proposes a facile approach for fabricating highly active electrocatalysts suitable for large-scale H2O2 production.