Oxygen Reduction Reaction Performance Research Articles

Tuning Two-Dimensional Phthalocyanine Dual Site Metal-Organic Framework Catalysts for the Oxygen Reduction Reaction.

Metal-organic frameworks (MOFs) offer an interesting opportunity for catalysis, particularly for metal-nitrogen-carbon (M-N-C) motifs by providing an organized porous structural pattern and well-defined active sites for the oxygen reduction reaction (ORR), a key need for hydrogen fuel cells and related sustainable energy technologies. In this work, we leverage electrochemical testing with computational models to study the electronic and structural properties in the MOF systems and their relationship to ORR activity and stability based on dual transitional metal centers. The MOFs consist of two M1 metals with amine nodes coordinated to a single M2 metal with a phthalocyanine linker, where M1/M2 = Co, Ni, or Cu. Co-based metal centers, in particular Ni-Co, demonstrate the highest overall activity of all nine tested MOFs. Computationally, we identify the dominance of Co sites, relative higher importance of the M2 site, and the role of layer M1 interactions on the ORR activity. Selectivity measurements indicate that M1 sites of MOFs, particularly Co, exhibit the lowest (<4%), and Ni demonstrates the highest (>46%) two-electron selectivity, in good agreement with computational studies. Direct in situ stability characterization, measuring dissolved metal ions, and calculations, using an alkaline stability metric, confirm that Co is the most stable metal in the MOF, while Cu exhibits notable instability at the M1. Overall, this study reveals how atomistic coupling of electronic and structural properties affects the ORR performance of dual site MOF catalysts and opens new avenues for the tunable design and future development of these systems for practical electrochemical applications.

Crystalline-Amorphous Heterophase PdMoCrW Tetrametallene: Highly Efficient Oxygen Reduction Electrocatalysts for a Long-Term Zn-Air Battery.

Metallenes have received sustained attention owing to their unique microstructure characteristics and compelling catalytic applications, but the synthesis of multielement crystalline-amorphous metallenes remains a formidable challenge. Herein, we report a one-step wet chemical reduction method to synthesize composition-tunable crystalline-amorphous heterophase PdMoCrW tetrametallene. As-synthesized PdMoCrW tetrametallene is composed of approximately six to seven atomic layers and has flexible crimpiness, a crystalline-amorphous heterophase structure, and high-valence metal species. Time-dependent experiments show that PdMoCrW tetrametallene follows a three-step growth mechanism that includes nucleation, lateral growth, and atom diffusion, respectively. The novel ultrathin structure, optimized Pd electronic structure, and hydrophilic surface together greatly promote the activity and stability of PdMoCrW tetrametallene in the alkaline oxygen reduction reaction. Pd75.9Mo9.4Cr8.9W5.8/C exhibits excellent mass and specific activities of 2.81 A mgPd-1 and 4.05 mA cm-2, which are 20.07/14.46 and 23.42/16.20 times higher than those of commercial Pt/C and Pd/C, respectively. Furthermore, a Zn-air battery assembled using Pd75.9Mo9.4Cr8.9W5.8/C as a cathode catalyst achieves a peak power density of 156 mW cm-2 and an ultralong durability of 329 h. This study reports an effective strategy for constructing crystalline-amorphous quaternary metallenes to advance non-Pt electrocatalysts toward oxygen reduction reaction (ORR) performance and for a Zn-air battery.

Time‐Resolved Oxidation State Changes Are Key to Elucidating the Bifunctionality of Perovskite Catalysts for Oxygen Evolution and Reduction

In a unified regenerative fuel cell (URFC) or reversible fuel cell, the oxygen bifunctional catalyst must switch reversibly between the oxygen reduction reaction (ORR), fuel cell mode, and the oxygen evolution reaction (OER), electrolyzer mode. However, it is often unclear what effect alternating between ORR and OER has on the electrochemical behavior and physiochemical properties of the catalyst. Herein, operando X‐ray absorption spectroscopy (XAS) is utilized to monitor the continuous and dynamic evolution of the Co, Mn, and Fe oxidation states of perovskite catalysts Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) and La0.4Sr0.6MnO3‐δ (LSM), while the potential is oscillated between reducing and oxidizing potentials with cyclic voltammetry. The results reveal the importance of investigating bifunctional catalysts by alternating between fuel cell and electrolyzer operation and highlight the limitations and challenges of bifunctional catalysts. It is shown that the requirements for ORR and OER performance are divergent and that the oxidative potentials of OER are detrimental to ORR activity. These findings are used to give guidelines for future bifunctional catalyst design. Additionally, it is demonstrated how sunlight can be used to reactivate the ORR activity of LSM after rigorous cycling.

Highly Dispersed Mn-Doped Ceria Supported on N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Reaction.

The weak adsorption of oxygen on transition metal oxide catalysts limits the improvement of their electrocatalytic oxygen reduction reaction (ORR) performance. Herein, a dopamine-assisted method is developed to prepare Mn-doped ceria supported on nitrogen-doped carbon nanotubes (Mn-Ce-NCNTs). The morphology, dispersion of Mn-doped ceria, composition, and oxygen vacancies of the as-prepared catalysts were analyzed using various technologies. The results show that Mn-doped ceria was formed and highly dispersed on NCNTs, on which oxygen vacancies are abundant. The as-prepared Mn-Ce-NCNTs exhibit a high ORR performance, on which the average electron transfer number is 3.86 and the current density is 24.4% higher than that of commercial 20 wt % Pt/C. The peak power density of Mn-Ce-NCNTs is 68.1 mW cm-2 at the current density of 138.9 mA cm-2 for a Zn-air battery, which is close to that of 20 wt % Pt/C (69.4 mW cm-2 at 106.1 mA cm-2). Density functional theory (DFT) calculations show that the oxygen vacancy formation energies of Mn-doped CeO2(111) and pure CeO2(111) are -0.55 and 2.14 eV, respectively. Meanwhile, compared with undoped CeO2(111) (-0.02 eV), Mn-doped CeO2(111) easily adsorbs oxygen with the oxygen adsorption energy of only -0.68 eV. This work provides insights into the synergetic effect of Mn-doped ceria for facilitating oxygen adsorption and enhancing ORR performance.

Iron-based graphene composite for oxygen reduction reaction in alkaline media: Electrocatalytic activity and lifetime evaluation

The development of electrocatalysts with high catalytic performance and low costs for oxygen reduction reaction (ORR) is still challenging. Herein, an overall solution for ORR in alkaline media, from the catalyst synthesis to catalyst regeneration and to the development of a rapid, reliable and easy approach for electrode surface evaluation, is presented. We focused on the development and characterization of an efficient material for ORR in alkaline media, α-Fe2O3 N-doped graphene (Fe-N-Gr). The associative pathway for the four electron transfer ORR mechanism is sustained by the Raman spectra recorded from the electrode surface. We highlighted the possibility of catalyst regeneration by a simple electrochemical method. After two regeneration rounds and 1500 cycles in O2-saturated 1 M NaOH, the catalyst still retains 40.8 % catalytic activity. Finally, as a part of the overall solution, we demonstrated that a methodology based on Raman spectroscopic measurements and machine learning algorithms can be applied for graphene-based catalysts lifetime investigation.

Electrocatalytic Oxygen Reduction Using Metastable Zirconium Suboxide

Strategies for discovery of high‐performance electrocatalysts are important to advance clean energy technologies. Metastable phases such as low temperature or interfacial structures that are difficult to access in bulk may offer such catalytically active surfaces. We report here that the suboxide Zr3O, which is formed at Zr‐ZrO2 interfaces but does not appear in the experimental Zr‐O phase diagram exhibits outstanding oxygen reduction reaction (ORR) performance surpassing that of benchmark Pt/C and most transition metal‐based catalysts. Addition of Fe3C nanoparticles to give a Zr‐Zr3O‐Fe3C/NC catalyst (NC = nitrogen‐doped carbon) gives a half‐wave potential (E1/2) of 0.914 V, outperforming Pt/C and showing only a 3 mV decrease after 20,000 electrochemical cycles. A zinc‐air battery (ZAB) using this cathode material has a high power density of 241.1 mW cm‐2 and remains stable for over 50 days of continuous cycling, demonstrating potential for practical applications. Zr3O demonstrates that interfacial or other phases that are difficult to stabilize may offer new directions for the discovery of high‐performance electrocatalysts.

Electrocatalytic Oxygen Reduction Using Metastable Zirconium Suboxide.

Strategies for discovery of high-performance electrocatalysts are important to advance clean energy technologies. Metastable phases such as low temperature or interfacial structures that are difficult to access in bulk may offer such catalytically active surfaces. We report here that the suboxide Zr3O, which is formed at Zr-ZrO2 interfaces but does not appear in the experimental Zr-O phase diagram exhibits outstanding oxygen reduction reaction (ORR) performance surpassing that of benchmark Pt/C and most transition metal-based catalysts. Addition of Fe3C nanoparticles to give a Zr-Zr3O-Fe3C/NC catalyst (NC = nitrogen-doped carbon) gives a half-wave potential (E1/2) of 0.914 V, outperforming Pt/C and showing only a 3 mV decrease after 20,000 electrochemical cycles. A zinc-air battery (ZAB) using this cathode material has a high power density of 241.1 mW cm-2 and remains stable for over 50 days of continuous cycling, demonstrating potential for practical applications. Zr3O demonstrates that interfacial or other phases that are difficult to stabilize may offer new directions for the discovery of high-performance electrocatalysts.

Simultaneous Mapping of Electrocatalytic Activity and Selectivity via Hybrid Scanning Electrochemical Probe Microscopy.

Nanoscale scanning electrochemical probe microscopy started to elucidate the heterogeneity of electrocatalytic activity at electrode surfaces. However, understanding the heterogeneity in product selectivity, another crucial aspect of interfacial reactivity, remains challenging. Herein, we introduce a method combining scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) to enable the spatially resolved mapping of both activity and selectivity in electrocatalysis. A dual-channel nanopipette probe was developed: one channel for activity mapping and the other for product detection with a high collection efficiency (>95%) and sensitivity. Simultaneous mapping of activity and selectivity in the oxygen reduction reaction (ORR) is demonstrated. Combined with colocalized crystal orientation mapping, we uncover the local electrocatalytic performance of ORR at different facets on polycrystalline Pt and Au. The high-resolution selectivity mapping enabled by our method with colocalized structural characterization can provide structure-activity-selectivity relationships that are often unavailable in ensemble measurement, holding promise for understanding key structural motifs controlling interfacial reactivity.

Single-atom Fe catalysts with pyrrolic-type FeN4 sites for efficient oxygen reduction reaction: Identifying the roles of different N species

Developing electrocatalysts with efficient cathode oxygen reduction reaction (ORR), for example, iron-based single-atom catalysts (Fe-SACs), has been deemed necessary to accelerate the commercialisation process of zinc (Zn)–air batteries. Nevertheless, determining how various nitrogen species and active metal centres coordinate on an atomic scale remains unclear and inadequately explained. Herein, we demonstrate a soft-template-aided technique using Fe-containing molecules (e.g. iron phthalocyanine [FePc], Fe-1,10-phenanthroline [Fe-Phen] and Fe-glucose) to enhance the performance of Fe-SACs in terms of ORR. In this technique, FePc molecules can be converted into atomically dispersed pyrrolic-type iron–nitrogen (FeN4) sites during a pyrolytic process. The resultant catalyst exhibits excellent ORR activity (half-wave potential = 0.90 V) in alkaline medium and standing battery performance when used in Zn–air batteries (peak power density = 197.3 mW cm−2 and specific capacity = 796.2 mAh g−1). As per the findings from control experiments and characterisation studies, electron transfer between the support and the active Fe centre amplifies the ORR performance. Theoretical calculations substantiate that Fe sites coordinated with pyrrolic N atoms govern the electronic configuration of the catalysis, reducing the free energy absorption of reaction intermediates and thus increasing its intrinsic ORR capability. Herein, we aim to offer a fresh perspective on the relation between coordination environments and catalytic activity in ORR catalysts.

Electron Transfer from Encapsulated Fe3C to the Outermost N‐Doped Carbon Layer for Superior ORR

AbstractEncapsulating Fe3C in carbon layers has emerged as an innovative strategy for protecting Fe3C while preserving its high oxygen reduction activity. However, fundamental questions persist regarding the active sites of encapsulated Fe3C due to the restricted accessibility of oxygen molecules to the metal sites. Herein, the intrinsic electron transfer mechanisms of Fe3C nanoparticles encapsulated in N‐doped carbon materials are unveiled for oxygen reduction electrocatalysis. The precision‐structured C1N1 material is used to synthesize N‐doped carbons with encapsulated Fe3C, significantly enhancing catalytic activity (EONSET = 0.98 V) and achieving near‐100% operational stability. In anion‐exchange membrane fuel cells, an excellent peak power density of 830 mW cm−2 is reached at 60 °C. The experimental and computational results revealed that the presence of Fe3C cores dynamically triggers electron transfer to the outermost carbon layer. This phenomenon amplifies the oxygen reduction reaction performance at N sites, contributing significantly to the observed catalytic enhancement.

Enhanced Mass Activity and Durability of Bimetallic Pt-Pd Nanoparticles on Sulfated-Zirconia-Doped Graphene Nanoplates for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cell Applications.

Developing highly active and durable Pt-based electrocatalysts is crucial for polymer electrolyte membrane fuel cells. This study focuses on the performance of oxygen reduction reaction (ORR) electrocatalysts composed of Pt-Pd alloy nanoparticles on graphene nanoplates (GNPs) anchored with sulfated zirconia nanoparticles. The results of field emission scanning electron microscopy and transmission electron microscopy showed that Pt-Pd and S-ZrO2 are well dispersed on the surface of the GNPs. X-ray diffraction revealed that the S-ZrO2 and Pt-Pd alloy coexist in the Pt-Pd/S-ZrO2-GNP nanocomposites without affecting the crystalline lattice of Pt and the graphitic structure of the GNPs. To evaluate the electrochemical activity and reaction kinetics for ORR, we performed cyclic voltammetry, rotating disc electrode, and EIS experiments in acidic solutions at room temperature. The findings showed that Pt-Pd/S-ZrO2-GNPs exhibited a better ORR performance than the Pt-Pd catalyst on the unsulfated ZrO2-GNP support and with Pt on S-ZrO2-GNPs and commercial Pt/C.

Carbon Corrosion Induced by Surface Defects Accelerates Degradation of Platinum/Graphene Catalysts in Oxygen Reduction Reaction.

Graphene supported electrocatalysts have demonstrated remarkable catalytic performance for oxygen reduction reaction (ORR). However, their durability and cycling performance are greatly limited by Oswald ripening of platinum (Pt) and graphene support corrosion. Moreover, comprehensive studies on the mechanisms of catalysts degradation under 0.6-1.6V versus RHE (Reversible Hydrogen Electrode) is still lacking. Herein, degradation mechanisms triggered by different defects on graphene supports are investigated by two cycling protocols. In the start-up/shutdown cycling (1.0-1.6V vs.RHE), carbon oxidation reaction (COR) leads to shedding or swarm-like aggregation of Pt nanoparticles (NPs). Theoretical simulation results show that the expansion of vacancy defects promotes reaction kinetics of the decisive step in COR, reducing its reaction overpotential. While under the load cycling (0.6-1.0V vs.RHE), oxygen containing defects lead to an elevated content of Pt in its oxidation state which intensifies Oswald ripening of Pt. The presence of vacancy defects can enhance the transfer of electrons from graphene to the Pt surface, reducing the d-band center of Pt and making it more difficult for the oxidation state of platinum to form in the cycling. This work will provide comprehensive understanding on Pt/Graphene catalysts degradation mechanisms.

WC nanoparticles and NiFe alloy co-encapsulated in N-doped carbon nanocage for exceptional OER and ORR bifunctional electrocatalysis

Developing earth-abundant electrocatalysts with optimized intrinsic active sites is crucial for enhancing bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) performance. In this study, we fabricated a hollow structured carbon framework utilizing NiFe Prussian Blue analogs (PBAs) as templates, while polypyrrole (PPy) and phosphotungstic acid (PW12). Pyrrole monomer underwent polymerization on the nanocubic PBA surface in the presence of PW12 (PBA@PPy-PW12). Subsequent carbothermal reduction created an N-doped carbon shell with embedded NiFe alloy and tungsten carbide (WC) nanoparticles. The polymeric PPy-PW12 nature can not only prevent the aggregation of PBA and WC structures but also enhance electrical conductivity by connecting neighboring nanospheres. Moreover, the introduction of WC can significantly enhance the bifunctional electrocatalytic activity of the carbon-based catalyst, which is attributed to synergism between the WC and NiFe materials within the NC layer. Consequently, NiFe/W0.3C@NC exhibited outstanding OER (overpotential = 290 mV for 10 mA/cm2; Tafel slope = 57 mV/dec) and ORR (half wave potential = 0.81 V; Tafel slope = 61 mV/dec) performances. This work presents a promising avenue for developing high-performance electrocatalysts for energy conversion systems that showcase remarkable efficiency, stability, and potential practicability.

In-situ immobilization strategy for single-atom iron sites to enhance oxygen reduction reaction in Zn–air batteries and microbial fuel cells

A straightforward and environmentally friendly approach was utilized to synthesize single-atomic Fe-N-C catalyst. In-situ immobilization of Fe3+ during the formation of polydopamine (PDA) and ZIF-8 in aqueous solution effectively prevent metal agglomeration. The mutual promotion of PDA and aqueous solution constructed the hybrid-level porous hollow structure in P-FeNC. This method extends the solution scope from organic solution system to water solution, thus providing fascinating opportunities for investigating metal-N-C catalyst by in-situ mixing various metal salt precursor and dopamine. The optimal P-FeNC catalyst demonstrates superlative oxygen reduction reaction (ORR) performance, with the half-wave potentials (E1/2) of 0.886 V, 0.790 V and 0.720 V in 0.1 M KOH, 0.5 M H2SO4 and 0.05 M PBS solutions, which exceeded commercial 20 wt% Pt/C. The combinatorial impacts of highly-dense FeN4 active sites and interconnected hierarchical mesopores/macropores are presumed to underpin the observed enhancement in ORR performance. Further evaluations show that the power densities of P-FeNC equipped zinc-air battery (ZAB) and microbial fuel cell (MFC) are 460 mW cm-2 and 3083 ± 10 mW m-2, respectively. This study confirms the feasibility to design the innovative single-atom catalyst in aqueous solution and provides constructive ideas to employ the high-performance P-FeNC electrocatalyst in ZABs and MFCs.

Resonant structure substrate anchors Pt to form ordered alloys for efficient oxygen reduction reaction

Platinum-based ordered alloys have excellent catalytic performance for the cathodic oxygen reduction reaction (ORR) in fuel cells. However, these alloys exhibit a lower degree of ordering and larger crystal grains after heat treatment. Herein, a series of cyanamide group molecules (cyanamide, dicyandiamide, melamine) was employed as substrates to modify Pt-based alloys by promoting the binding between metal ions, leading to the preparation of ∼ 4 nm PtM (M = Co, Fe, Ni) ordered alloys after heat treatment. Among them, the PtCo ordered alloy prepared using hydrolyzed cyanamide with a unique resonance structure exhibits a high degree of order (93.1 %), and its mass activity of 0.915 A mgPt-1 at 0.9 V is superior to that of Pt/C. The theoretically calculated adsorption energies of these alloys demonstrate that the resonance structure of the cyanamide substrate is beneficial for alloy formation, thereby facilitating ordered alloy synthesis.

A medium-entropy engineered double perovskite oxide for efficient and CO2-tolerant cathode of solid oxide fuel cells

Developing highly active and robust cathodes remains challenging for solid oxide fuel cells (SOFCs). Therefore, we report an A-site medium-entropy double perovskite oxide PrBa0.5Sr0.25Ca0.2Ce0.05Co2O5+δ (PBSCCC) and its electrocatalytic activity and CO2 tolerance property are systematically probed. The PBSCCC cathode exhibits excellent oxygen reduction reaction (ORR) activity with a low polarization resistance of 0.027 Ω cm2 at 700 °C. More importantly, compared to PrBaCo2O5+δ (PBC) and PrBa0.8Ca0.2Co2O5+δ (PBCC) oxides, its CO2 resistance is prominently enhanced with significantly less BaCO3 and Co3O4 impurities formed. The superior ORR performance and structure stability are mainly attributed to its high electrical conductivity and significantly reduced surface cation segregations. Our results show that the potential of PBSCCC as a cathode material for SOFCs is enormous and also prove the rationality and feasibility of entropy engineering for cathode development.

Efficient and durable oxygen reduction in alkaline media by doping heteroatomic boron into FeSA-NC catalyst

Despite extensive research has been conducted on atomic dispersion catalysts for various reactions, altering the electronic structure of the central metal to enhance electrochemical reactivity remains a challenging task. Herein, the electrochemical reactivity was considerably enhanced by introducing heteroatomic B to adjust the d-band of single Fe center. In specific, the obtained FeSA-BNC catalyst demonstrated an outstanding ORR performance (E1/2 = 0.87 V) and exhibited greater long-term durability in alkaline media compared to Pt/C. The performance of FeSA-BNC in Zn–air battery was also higher than that of Pt/C. According to theoretical calculations, a downward shift in the d-band center of Fe was induced by introducing B, thereby improving the desorption of intermediates and facilitating the oxygen reduction reaction (ORR).

Covalent organic frameworks derived Single-Atom cobalt catalysts for boosting oxygen reduction reaction in rechargeable Zn-Air batteries

The design and development of high-performance and long-life Pt-free catalysts for the oxygen reduction reaction (ORR) is of great important with respect to metal-air batteries and fuel cells. Herein, a new low-cost covalent organic frameworks (COFs)-derived CoNC single-atoms catalyst (SAC) is fabricated and compared with the engineered nanoparticle (NP) counterpart for ORR activity. The ORR performance of the SAC catalyst (CoSA@NC) surpasses the NP counterpart (CoNP-NC) under the same operation condition. CoSA@NC also achieves improved long-term durability and better methanol tolerance compared with the Pt/C. The zinc-air battery assembled by the CoSA@NC cathode delivers a higher power density and energy density than that of commercial Pt/C catalyst. Molecular dynamics (MD) is performed to explain the spontaneous evolution from clusters to single-atom metal configuration and density functional theory (DFT) calculations find that CoSA@NC possesses lower d-band center, resulting in weaker interaction between the surface and the O-containing intermediates. Consequently, the reductive desorption of OH*, the rate-determine step, is further accelerated.

Flexible Zn-air battery for self-powered aptasensing SARS-CoV-2

It is vital to manufacture the highly efficient flexible and readable self-powered electrochemical aptasensor for the sensitive and selective detection of SARS-CoV-2 S-gene respiratory diseases. In this work, a Zn-air battery (ZAB) was assembled using hollow mesocarbon spheres enveloped with Co-N-C atomic sites (referred to as Co-N-C@mHCSs) as the cathode electrocatalyst and utilized it as the ZAB-driven self-powered aptasensor (SPA) for sensitively and selectively detecting SARS-CoV-2 S-gene from complicated environments. The flexible Co-N-C@mHCS-assembled ZAB had a high open-circuit voltage of 1.411V and a significant output maximum power density of 178.4mWcm–2 due to the improved oxygen reduction reaction performance. With a SARS-CoV-2 S gene concentration range of 1.0 fg mL–1 to 10ngmL–1 and an ultralow detection limit of 0.45 fg mL–1, the developed ZAB-SPA displayed strong selectivity, good stability, and exceptional repeatability. The established ZAB-SPA also offered a broad range of practicability for the on-site detection of the SARS-CoV-2 S-gene by using a mobile phone, as well as promising applicability in a crowded environment.

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.