Selective Reduction Of O2 Research Articles

Undervalued role of metal-carbon junction in selective generation of H2O2: An example of the zinc-carbon junction edge providing asymmetric active sites for efficient oxygen reduction

The spontaneous oxygen reduction is a potential technology for in-situ H2O2 production, which gets rid of the dependence on electricity and solar energy. Previous some metal–carbon compounds reported are feasible to trigger oxygen reduction. These reports always claim the high H2O2 generation ability of metal–carbon composites, while rarely discuss the contribution of carbon and the carbon–metal junction to the oxygen reduction process. Inspired by the dual active sites, we infer that the role of interfacial carbon in metal–carbon composites is underestimated. By a heat treatment of the co-precipitate of zinc and glucose, the Zn-C junction is constructed in Zn-gc to achieve a spontaneous selective reduction of O2 to H2O2. The Zn-C interface edge is active site, where an asymmetric activation is achieved by bonding two O atoms from O2 to C and Zn, respectively. The Zn traction to one of the O atoms is mainly in xy plane, while the C traction to the other O atom is parallel to z-axis. The yield of H2O2 produced per gram of Zn increases from 27.89 mg to 122.21 mg, an improvement of 4.38 times. And the inertness of Zn and its oxygen-containing compounds towards H2O2 enables Zn-gc/O2 system to stabilize H2O2 over a long period of time. This work reveals the crucial role of neglected junction interfaces in oxygen reduction reactions in metal–carbon composites.

Self-assembled S-scheme In2.77S4/K+-doped g-C3N4 photocatalyst with selective O2 reduction pathway for efficient H2O2 production using water and air

Self-assembled S-scheme In2.77S4/K+-doped g-C3N4 photocatalyst with selective O2 reduction pathway for efficient H2O2 production using water and air

Insulated π-Conjugated Azido Scaffolds for Stepwise Functionalization via Huisgen Cycloaddition on Metal Oxide Surfaces.

In organic-inorganic hybrid devices, fine interfacial controls by organic components directly affect the device performance. However, fabrication of uniformed interfaces using π-conjugated molecules remains challenging due to facile aggregation by their strong π-π interaction. In this report, a π-conjugated scaffold insulated by covalently linked permethylated α-cyclodextrin moiety with an azido group is synthesized for surface Huisgen cycloaddition on metal oxides. Fourier-transformed infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy confirm the successful immobilization of the insulated azido scaffold on ZnO nanowire array surfaces. Owing to the highly independent immobilization, the scaffold allows rapid and complete conversion of the surface azido group in Huisgen cycloaddition reactions with ethynyl-terminated molecules, as confirmed by FT-IR spectroscopy monitoring. Cyclic voltammetry analysis of modified indium tin oxide substrates shows the positive effects of cyclic insulation toward suppression of intermolecular interaction between molecules introduced by the surface Huisgen cycloaddition reactions. The utility of the scaffold for heterogeneous catalysis is demonstrated in electrocatalytic selective O2 reduction to H2O2 with cobalt(II) chlorin modified fluorine doped tin oxide electrode and photocatalytic H2 generation with iridium(III) dye-sensitized Pt-loadedTiO2 nanoparticle. These results highlight the potential of the insulated azido scaffold for a stepwise functionalization process, enabling precise and well-defined hybrid interfaces.

MOF-derived CuO@CB@CF cathode for O2 activation to generate ROSs for efficient electro-Fenton-catalysis

The generation of reactive radicals by molecular oxygen activation has become an important advanced oxidation technique. The combination of highly active carbon materials and stable transition metal oxides can activate molecular oxygen to produce hydrogen peroxide and further produce active free radicals at the same time, which is an efficient way for the removal of organic pollutants by heterogeneous electro-Fenton (HEF) system. In this study, a novel metal organic framework (MOF) derived CuO-carbon black-carbon felt (CuO@CB@CF) composite catalytic electrode has been prepared, which can generate H2O2 efficiently by selective O2 reduction through two-electron pathway with high pollutant removal efficiency. By optimizing the calcination temperature of MOF and loading capacity, the MOF-derived CuO@CB@CF has demonstrated excellent performance as a HEF catalytic electrode. Meanwhile, the effects of applied voltage, pH value, electrode area and aeration conditions have been studied. The excellent performance of MOF-derived CuO@CB@CF provides new insights into the removal of organic pollutants through electro-Fenton processes of transition metal oxide and carbon-based catalysts.

A neoteric antibacterial ceria-silver nanozyme for abiotic surfaces

Community-associated and hospital-acquired infections caused by bacteria continue to yield major global challenges to human health. Bacterial contamination on abiotic surfaces is largely spread via high-touch surfaces and contemporary standard disinfection practices show limited efficacy, resulting in unsatisfactory therapeutic outcomes. New strategies that offer non-specific and broad protection are urgently needed. Herein, we report our novel ceria-silver nanozyme engineered at a molar ratio of 5:1 and with a higher trivalent (Ce3+) surface fraction. Our results reveal potent levels of surface catalytic activity on both wet and dry surfaces, with rapid, and complete eradication of Pseudomonas aeruginosa, Staphylococcus aureus, and methicillin resistant S. aureus, in both planktonic and biofilm form. Preferential electrostatic adherence of anionic bacteria to the cationic nanozyme surface leads to a catastrophic loss in both aerobic and anaerobic respiration, DNA damage, osmodysregulation, and finally, programmed bacterial lysis. Our data reveal several unique mechanistic avenues of synergistic ceria-Ag efficacy. Ag potentially increases the presence of Ce3+ sites at the ceria-Ag interface, thereby facilitating the formation of harmful H2O2, followed by likely permeation across the cell wall. Further, a weakened Ag-induced Ce–O bond may drive electron transfer from the Ec band to O2, thereby further facilitating the selective reduction of O2 toward H2O2 formation. Ag destabilizes the surface adsorption of molecular H2O2, potentially leading to higher concentrations of free H2O2 adjacent to bacteria. To this end, our results show that H2O2 and/or NO/NO2−/NO3− are the key liberators of antibacterial activity, with a limited immediate role being offered by nanozyme-induced ROS including O2•- and OH•, and likely other light-activated radicals. A mini-pilot proof-of-concept study performed in a pediatric dental clinic setting confirms residual, and continual nanozyme antibacterial efficacy over a 28-day period. These findings open a new approach to alleviate infections caused by bacteria for use on high-touch hard surfaces.

Humic substances mediated superior photochemical pollutant conversion on defective TiO2 in environmentally relevant matrices: The key roles of oxygen vacancy in surface interactions, oxidant activation and radical generation

Ubiquitous humic substances usually exhibit strong interfering effects on target pollutant removal in advanced water purification. This work aims to develop a photochemical conversion system on the nonstoichiometric TiO2 for pollutant removal in environmentally relevant matrices. In this synergistic reaction system, the redox-reactive humic substances and defective oxygen vacancies can serve as the organic electron transfer mediator and the key surface reactive sites, respectively. This system achieves a superior pollutant degradation in real surface water at low oxidant concentrations. Reactive oxygen vacancies on the TiO2 surface and sub-surface are of considerable interest for this photochemical reaction system. By engineering defective oxygen vacancies on high-energy {001} polar facet, the surface and electronic interactions between tailored TiO2 and humic substances are greatly strengthened for the promoted electron transfer and oxidant activation. Rendered by the strong surface affinity and molecular activation, defective oxygen vacancies thermodynamically and dynamically promote reactive chain reactions for free radical formation, including the selective O2 reduction to ·O2− and the H2O2 activation to ·OH. Our findings take new insights into environmental geochemistry, and provide an effective strategy to in-situ boost the humic substances-mediated water purification without secondary pollution. Environmental implicationHumic substances are widely distributed in aquatic environment, thus playing important roles in environmental geochemistry. For example, humic substances can achieve good surface adsorption through electrostatic adsorption, ligand exchange and electronic interactions with typical TiO2 to form reactive ligand-metal charge transfer complexes for pollutant degradation. Inspired by the unique properties of surface and sub-surface oxygen vacancies, the defective TiO2 was designed to refine the humic substances-mediated photochemical reactions. A superior reactivity was measured for pollutant degradation. Our findings provide an effective strategy to boost naturally photochemical decontamination in environmentally relevant matrices.

Exploring the Impact of DAHP Impregnation on Activated Carbon Fibers for Efficient Charge Storage and Selective O2 Reduction to Peroxide

Understanding the properties and behavior of carbon materials is of paramount importance in the pursuit of sustainable energy solutions and technological advancements. As versatile and abundant resources, carbon materials play a central role in various energy conversion and storage applications, making them essential components in the transition toward a greener and more efficient future. This study explores the impact of diammonium hydrogen phosphate (DAHP) impregnation on activated carbon fibers (ACFs) for efficient energy storage and conversion applications. The viscose fibers were impregnated with varying DAHP concentrations, followed by carbonization and activation processes. The capacitance measurements were conducted in 6 mol dm−3 KOH, 0.5 mol dm−3 H2SO4, and 2 mol dm−3 KNO3 solutions, while the oxygen reduction reaction (ORR) measurements were performed in O2-saturated 0.1 mol dm−3 KOH solution. We find that the presented materials display specific capacitances up to 160 F g−1 when the DAHP concentration is in the range of 1.0 to 2.5%. Moreover, for the samples with lower DAHP concentrations, highly selective O2 reduction to peroxide was achieved while maintaining low ORR onset potentials. Thus, by impregnating viscose fibers with DAHP, it is possible to tune their electrochemical properties while increasing the yield, enabling the more sustainable and energy-efficient synthesis of advanced materials for energy conversion applications.

Single‐Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2O2 Production

AbstractPrecise manipulation of the coordination environment of single‐atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two‐step strategy to fabricate a series of hollow carbon‐based SACs featuring asymmetric Zn−N2O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn−N2O2−S). Systematic analyses demonstrate that the synergetic effects between the N2O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2O2. Remarkably, the Zn−N2O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2O2 generation. Consequently, the Zn−N2O2−S SAC exhibits impressive electrochemical H2O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm−2 in the flow cell, it shows a high H2O2 production rate of 6.924 mol gcat−1 h−1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h.

Single-Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2 O2 Production.

Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn-N2 O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn-N2 O2 -S). Systematic analyses demonstrate that the synergetic effects between the N2 O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2 O2 . Remarkably, the Zn-N2 O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2 O2 generation. Consequently, the Zn-N2 O2 -S SAC exhibits impressive electrochemical H2 O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm-2 in the flow cell, it shows a high H2 O2 production rate of 6.924 mol gcat -1 h-1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h.

A Cobalt(III) Corrole with a Tethered Imidazole for Boosted Electrocatalytic Oxygen Reduction Reaction

Comprehensive SummaryDeveloping electrocatalysts with high activity and selectivity for the oxygen reduction reaction (ORR) is vital to promote the performance of the next‐generation energy technologies, which depend on the efficiency of the catalytic reduction of dioxygen. In the structure of cytochrome c oxidases (CcOs), a histidine imidazole residue binding to the axial position of Fe plays a crucial role in facilitating the selective reduction of O2 to water. Inspired by nature, we herein report on the synthesis of CoIII corrole 1 tethered with an imidazole ligand as well as its electrocatalytic ORR and O2 binding features. As compared to the imidazolium‐free analogue, complex 1 displayed remarkably boosted activity for the selective four‐electron/four‐proton (4e‐/4H+) ORR with a half‐wave potential of E1/2 = 0.82 V versus reversible hydrogen electrode (RHE) in 0.1 mol/L KOH solutions. Importantly, we demonstrate that the tethered axial imidazole ligand improves the O2 binding ability of 1 thermodynamically and dynamically, which is crucial to boost electrocatalytic ORR performance. This work presents an example to improve electrocatalytic ORR activity and selectivity of Co corroles by introducing an axial imidazole ligand to enhance the O2 binding and activation.

P-Block Bismuth Nanoclusters Sites Activated by Atomically Dispersed Bismuth for Tandem Boosting Electrocatalytic Hydrogen Peroxide Production.

Constructing electrocatalysts with p-block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p-block-element bismuth-based (Bi-based) catalyst with the co-existence of single-atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Biclu ) (collectively denoted as BiOSSA /Biclu ) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H2 O2 ). As a result, BiOSSA /Biclu gives a high H2 O2 selectivity of 95 % in rotating ring-disk electrode, and a large current density of 36 mA cm-2 at 0.15 V vs. RHE, a considerable H2 O2 yield of 11.5 mg cm-2 h-1 with high H2 O2 Faraday efficiency of ∼90 % at 0.3 V vs. RHE and a long-term durability of ∼22 h in H-cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOSSA /Biclu , the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p-block-element Bi catalysts featuring atomic-level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p-block metals.

Electronic Structure Regulation of Single-Atom Catalysts for Electrochemical Oxygen Reduction to H2 O2.

Electrochemical synthesis of hydrogen peroxide (H2 O2 ) via the 2-electron oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process and catalysts combining high selectivity with superior activity are crucial for enhancing the efficiency of H2 O2 electrosynthesis. In recent years, single-atom catalysts (SACs) with the merits of maximum atom utilization efficiency, tunable electronic structure, and high mass activity have attracted extensive attention for the selective reduction of O2 to H2 O2 . Although considerable improvements are made in the performance of SACs toward the 2-electron ORR process, the principles for modulating the catalytic properties of SACs by adjusting the electronic structure remain elusive. In this review, the regulation strategies for optimizing the 2-electron ORR activity and selectivity of SACs by different methods of electronic structure tuning, including the altering of the central metal atoms, the modulation of the coordinated atoms, the substrate effect, and alloy engineering are summarized. Finally, the challenges and future prospects of advanced SACs for H2 O2 electrosynthesis via the 2-electron ORR process are proposed.

Effect of inorganic ions on H2O2 production over illuminated Au/WO3 with visible light

Production of H2O2 via semiconductor photocatalysis has received an increasing attention. Herein the effects of cations in perchlorate form and anions in sodium form are examined. Experiment was conducted with Au/WO3 under visible light in presence of methanol. The production of H2O2 was greatly promoted by A (Ni2+, PO43−, CO32−, and F−), slightly increased by B (SO42−, NO3−, Cl−, and ClO4−), greatly inhibited by C (Cu2+, and Fe3+), and slightly decreased by Co2+. Moreover, the effect of Ni2+ was weakening by F−, and vice versa. Analysis showed that Ni2+ was oxidized into Ni3+, reactive to methanol, not to water. On Au/WO3 electrode, anions A inhibited O2 reduction, and promoted methanol photo-oxidation, while all anions had little influence on the pathway of O2 reduction. A plausible mechanism is proposed, involving the hole oxidation of anions (not F−), followed by methanol oxidation. This work highlights the importance of inorganic ions to the selective reduction of O2.

(Invited) Thermoplasmonic Generation of Carbon Nanohydrids for Enhanced Electrocatalysis

Local heating from plasmonic nanostructures has shown great potential in photothermal therapy, optical trapping, heterogeneous catalysis, and synthesis of nanostructures. Titanium nitride (TiN) is one the most promising plasmonic materials for thermal applications (thermoplasmonics) due to its high thermostability (i.e.refractory), CMOS compatibility, and resistance to chemically harsh environments. On the other hand, hydrogen peroxide (H2O2) has a large annual production approaching 4 ×106 tons worldwide and the selective reduction of O2 via electrochemical oxygen reduction reaction (ORR) using renewable electricity is a promising way for H2O2 production. Carbon-based materials have shown great potential for the two-electron ORR to hydrogen peroxide. In this contribution, I will show a general approach to use the highly intense local temperature generated from plasmonic TiN nanocrystals for generating TiN/carbon nanohybrids that show enhanced efficiency and selectivity toward the ORR. The general applicability of plasmon-driven synthesis of nanocarbons to electrocatalysis will be discussed.

High-Efficient Generation of H2O2 by Aluminum-Graphite Composite through Selective Oxygen Reduction for Degradation of Organic Contaminants.

Hydrogen peroxide (H2O2) is an effective green oxidant, which has been widely applied for environmental remediation. Here, we prepared a novel aluminum-graphite (Al-Gr) composite, which was capable of high-efficient production of H2O2 through selective O2 reduction via a two-electron pathway. We discovered the production of H2O2 at a wide pH range, which could be enhanced by optimizing Al-Gr synthesis conditions. Poly(ethylene glycol) (PEG) addition could promote the formation of a welding interface and porous structure between Al and Gr in the Al-Gr composite, which enhanced the galvanic corrosion of Al0, the selectivity of oxygen reduction via the two-electron pathway, and the mass transfer of O2 in the Al-Gr/O2 system. The formation of Al4C3 could be regulated by sintering temperature and sintering time, which could promote the intergranular corrosion of Al0 and enhance the mass transfer of O2 by reaction with water to generate the porous structure in the Al-Gr composite. The concentration of H2O2 reached 777.5 mg/L at an initial pH of 9.0, an Al-Gr dosage of 8 g/L, and an O2 gas flow rate of 400 mL/min. The possible mechanisms of Al-Gr synthesis and H2O2 production in the Al-Gr/O2 system were proposed. The Al-Gr composite was effective for the in situ production of H2O2, which could be further decomposed into a hydroxyl radical (•OH) by Al0 in the Al-Gr composite. This composite could be used not only to decolorize the Rhodamine B dye but also to degrade various organic contaminants in different water matrices, indicating its environmental significance.

(Invited) Thermoplasmonic Generation of Carbon Nanohydrids for the Oxygen Reduction Reaction

Local heating from plasmonic nanostructures has shown great potential in photothermal therapy, optical trapping, heterogeneous catalysis, and synthesis of nanostructures. Titanium nitride (TiN) is one the most promising plasmonic materials for thermal applications (thermoplasmonics) due to its high thermostability (i.e. refractory), CMOS compatibility, and resistance in chemically harsh environments. On the other hand, hydrogen peroxide (H2O2) has a large annual production approaching 4 ×106 tons worldwide and the selective reduction of O2 via electrochemical oxygen reduction reaction (ORR) using renewable electricity is a promising way for H2O2 production. Carbon-based materials have shown great potential for the two-electron ORR to hydrogen peroxide. In this contribution, I will show a general approach to use the highly intense local temperature generated from plasmonic TiN nanocrystals for generating TiN/carbon nanohybrids that show enhanced efficiency and selectivity toward the ORR. The general applicability of plasmon-driven synthesis of nanocarbons to electrocatalysis will be discussed.

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

AbstractWe report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide.

We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2 O2 . We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90-100 % H2 O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2 O2 and H2 O. Bimolecular pathways have been implicated in facilitating H2 O formation, therefore, we attribute this high H2 O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host-guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.

Trimetallic Mn‐Fe‐Ni Oxide Nanoparticles Supported on Multi‐Walled Carbon Nanotubes as High‐Performance Bifunctional ORR/OER Electrocatalyst in Alkaline Media

AbstractDiscovering precious metal‐free electrocatalysts exhibiting high activity and stability toward both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions remains one of the main challenges for the development of reversible oxygen electrodes in rechargeable metal–air batteries and reversible electrolyzer/fuel cell systems. Herein, a highly active OER catalyst, Fe0.3Ni0.7OX supported on oxygen‐functionalized multi‐walled carbon nanotubes, is substantially activated into a bifunctional ORR/OER catalyst by means of additional incorporation of MnOX. The carbon nanotube‐supported trimetallic (Mn‐Ni‐Fe) oxide catalyst achieves remarkably low ORR and OER overpotentials with a low reversible ORR/OER overvoltage of only 0.73 V, as well as selective reduction of O2 predominantly to OH−. It is shown by means of rotating disk electrode and rotating ring disk electrode voltammetry that the combination of earth‐abundant transition metal oxides leads to strong synergistic interactions modulating catalytic activity. The applicability of the prepared catalyst for reversible ORR/OER electrocatalysis is evaluated by means of a four‐electrode configuration cell assembly comprising an integrated two‐layer bifunctional ORR/OER electrode system with the individual layers dedicated for the ORR and the OER to prevent deactivation of the ORR activity as commonly observed in single‐layer bifunctional ORR/OER electrodes after OER polarization.

Selective H2O2 production on N-doped porous carbon from direct carbonization of metal organic frameworks for electro-Fenton mineralization of antibiotics

Cathode materials with high activity, selectivity and stability are essential to efficient electrochemical H2O2 generation. Herein, nitrogen-doped porous carbon (NPC) is synthesized via direct calcination of nitrogen-containing metal organic framework. The N doping into porous carbon boosts H2O2 generation, thus enhancing electro-Fenton activity. The NPC cathode exhibits a highly selective reduction of O2 to H2O2 (96.4% at pH 1 and −0.1 V vs SCE) and H2O2 production rate reaches 52.3 mmol·L−1 h−1 (pH 1, −0.6 V vs SCE). Moreover, NPC achieves a high current efficiency of 87.7% for H2O2 production (pH 1, −0.5 V vs SCE). The removal efficiency of oxcarbazepine antibiotics achieves 100% in 10 min ([Fe2+] = 1.0 mmol L−1, C0 = 12.61 mg L−1 (50 μmol L−1), pH 1–5, −0.5 V vs SCE), and total organic carbon (TOC) removal efficiency reaches 90.7% in 60 min. Additionally, the removal efficiency of other antibiotics of prednisolone, chloramphenicol and thiamphenicol reaches 97.0–98.8% in 10 min and the TOC removal efficiency achieves 70.8–92.0% in 60 min. Moreover, NPC shows an excellent electrochemical stability. This work is valuable for designing electro-Fenton catalysts with high activity, selectivity and stability.