Oxygen Reduction Reaction Performance Research Articles

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction

Nanographenes are among the fastest‐growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal‐based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2‐conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes’ ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction.

Nanographenes are among the fastest-growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal-based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2-conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes' ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Bamboo-derived aerogel with atomically dispersed Co as a high-performance bifunctional electrocatalyst for durable zinc-air batteries

The development of highly efficient and durable bifunctional electrocatalysts is crucial for rechargeable zinc-air batteries, which have garnered significant attention as a promising sustainable energy storage technology. Herein, a novel Co-N-C-1050 catalyst is synthesized using a high-temperature gas transport method, where high purity cobalt powder and bamboo biomass aerogel are treated with ammonia gas at 1050 °C. The resulting catalyst exhibits a 3D interconnected porous network composed of dense carbon fibers, which atomically dispersed Co, N, and C elements are uniformly distributed. The synergistic integration of highly active Co single atoms and N-doped 3D carbon fiber aerogel enables Co-N-C-1050 to demonstrate excellent bifunctional electrocatalytic performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), comparable to commercial Pt/C and RuO2 catalysts. This catalyst has a half-wave potential of 0.842 V for ORR and a potential of 1.472 V at 10 mA cm−2 for OER, outperforming N-C-1050 and benchmark catalysts. A zinc-air battery is driven by Co-N-C-1050 achieves a high power density of 135 mW/cm2 and exceptional stability over 138 h of charge/discharge cycling, surpassing the higher-cost Pt/C + RuO2 catalyst. This biomass aerogel based single-site Co-N-C catalyst offers a promising approach for developing high-efficiency and long-cycle-life zinc-air batteries.

DFT-guided synthesis of N, B dual-doped porous carbon from saccharina japonica for enhanced oxygen reduction catalysis

IntroductionThe oxygen reduction reaction (ORR) is a crucial determinant of the energy transformation capacity of fuel cells. This study investigates the performance of N and B dual-doped carbon in ORR.MethodsSix models using density functional theory (DFT) are developed to compare the performance of different doping strategies. A highly efficient dual-doped carbon ORR catalyst (S-850-1) is synthesized from Saccharina japonica, containing 4.54 at% N and 1.05 at% B atom.ResultsElectrochemical analysis reveals that S-850-1 significantly outperforms the nitrogen mono-doped carbon S-850, exhibiting a higher half-wave potential of 0.861 V and a greater limited current density of −5.60 mA cm⁻2, compared to S-850’s 0.838 V and −5.24 mA cm⁻2. Furthermore, S-850-1 surpasses the performance of 20% Pt/C, demonstrating enhanced durability and exceptional resistance to CO and methanol. The 1.40 V open circuit voltage produced by S-850-1 when integrated into a Zn-air battery can power an LED light.DiscussionBoth theoretical and practical evaluations validate the excellent ORR performance of nitrogen and boron dual-doped carbon, as evidenced by the agreement between the electrochemical results and DFT calculations. This work not only extends the range of ORR catalysts derived from biomass but also provides guidance on creating and producing affordable, effective catalysts that utilize natural resources.

Optimizing Fe-N-C Electrocatalysts for PEMFCs: Influence of Constituents and Pyrolysis on Properties and Performance

Proton exchange membrane fuel cells (PEMFCs) are promising alternative technologies with applications in stationary power systems, vehicles, and portable electronics due to their low temperature operation, fast start-up, and environmental advantages. However, the high cost of platinum-based catalysts, in particular for the oxygen reduction reaction (ORR) of the cathode side, prevents their widespread incorporation. Fe-N-C electrocatalysts have emerged as viable alternatives to platinum. In this study, different precursor components were investigated for the way that they affect the pyrolysis process, which is crucial for tailoring the final catalyst properties. In particular, carbon allotropes such as carbon Vulcan, Ketjenblack, and carbon nanotubes were selected for their unique structures and properties. In addition, various sources of iron (FeCl2, FeCl3, and K[Fe(SCN)4]) were evaluated. The influence of the pyrolysis atmosphere on the resulting Fe-N-C catalyst structures was also assessed. Through an integrated structure and surface chemistry analyses, as well as electrochemical tests with rotating disk electrode experiments in acidic media, the ORR performance and stability of these catalysts were defined. By examining the relationships between carbon sources and iron precursors, this research provides valuable information for the optimization of Fe-N-C catalysts in fuel cell applications.

Heteroatoms doping for modulation of sp3-hybridized carbon sites for highly efficient bio-electroreduction of oxygen in microbial fuel cells

Due to the fact that single chamber microbial fuel cells (SC-MFCs) generally require efficient, stable, and inexpensive cathode catalysts to promote bioelectricity generation performance, metal-free catalysts have attracted increasing attention in SC-MFCs. However, enhancing the electrocatalytic activity of the oxygen reduction reaction (ORR) using metal-free catalysts remains a challenge. This study introduces a metal-free porous catalyst by synchronously doping phosphorus (P) and nitrogen (N) atoms into the biomass-derived carbon skeleton (AB-N-P). The AB-N-P catalyst, displaying half-wave potentials (E1/2) of 0.89 (alkaline) and 0.832 V (neutral), exhibits superior ORR performances compared to most metal-free catalysts and is comparable to some non-precious metal catalysts. Remarkably, it (E1/2: 0.890 to 0.880 V) matches or even exceeds the stability of commercial Pt/C catalyst (E1/2: 0.864 to 0.849 V) after 3000 cyclic voltammetry cycles. Density functional theory (DFT) calculations demonstrate that P and N co-doping synergistically increases the sp3-hybridized carbon content and redistributes charge density, thereby enhancing the catalytic properties and altering the electronic properties of the active sites. In practical applications in SC-MFCs, the AB-N-P electrocatalyst shows exceptional performance, achieving a higher power density (896.4 mW m−2) than that of commercial Pt/C (538.2 mW m−2). This study offers insightful revelations into the modulation of carbon active-sites by doping heteroatoms to carbon skeleton as metal-free catalyst in bioenergy-generation systems.

Axial Coordination Engineering on Fe-N-C Materials for Oxygen Reduction: Insights from Theory.

Axial coordination engineering has emerged as an effective strategy to regulate the catalytic performance of metal-N-C materials for oxygen reduction reaction (ORR). However, the ORR mechanism and activity changes of their active centers modified by axial ligands are still unclear. Here, a comprehensive investigation of the ORR on a series of FeN4-L moieties (L stands for an axial ligand) is performed using advanced density functional theory (DFT) calculations. The axial ligand has a substantial effect on the electronic structure and catalytic activity of the FeN4 center. Specially, FeN4-C6H5 is screened as a promising active moiety with superior ORR activity, as further revealed by constant-potential calculations and kinetic analysis. The enhanced activity is attributed to the weakened *OH adsorption caused by the altered electronic structure. Moreover, microkinetic modeling shows that at pH=1, FeN4-C6H5 possesses an impressive theoretical half-wave potential of ~1.01 V, superior to the pristine Fe-N-C catalysts (~0.88 V) calculated at the same level. These findings advance the understanding of the ORR mechanism of FeN4-L and provide guidance for optimizing the ORR performance of single-metal-atom catalysts.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High-Performance Oxygen Reduction Reaction Activity for Quasi-Solid-State Rechargeable Zn-Air Batteries.

Dimeric metal sites (DiMSs) in carbon-based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs-based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe-N/CBs) are prepared using the precursor of metal-organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe-N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half-wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager-type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi-solid-state Zn-air batteries assembled using DiFe-N/CBs-based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High‐Performance Oxygen Reduction Reaction Activity for Quasi‐Solid‐State Rechargeable Zn‐Air Batteries

AbstractDimeric metal sites (DiMSs) in carbon‐based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs‐based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe‐N/CBs) are prepared using the precursor of metal‐organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe‐N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half‐wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager‐type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi‐solid‐state Zn‐air batteries assembled using DiFe‐N/CBs‐based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Surface‐Engineered Pt‐Ni(111) Nanocatalysts for Boosting Their ORR Performance via Thermal Treatment

AbstractThe electrochemical oxygen reduction reaction (ORR) is critical for fuel cell application, and modifying surface structures of electrocatalysts has proven effective in improving their catalytic performances. In this study, we investigated surface‐engineered Pt−Ni nano‐octahedra subjected to annealing in various atmospheres. All octahedral nanocrystals retained their Pt−Ni {111} facets at an elevated temperature following the annealing treatments. Air annealing led to the formation of nickel‐rich shells on the Pt−Ni surface. In contrast, hydrogen (H₂) as a reducing gas facilitated the reduction of surface Ni species, incorporating them into the Pt−Ni bulk alloy, which resulted in superior mass activity and specific activity for ORR‐approximately 2.4 and 2.3 times as high as those from the unmodified counterpart, respectively. After 20,000 potential cycles, the H₂/Ar‐annealed Pt−Ni nano‐octahedra maintained a mass activity of 3.92 A/ , surpassing the initial mass activity of the unannealed counterparts (2.95 A/ ). These findings demonstrate a viable approach for tailoring catalyst surfaces to enhance performance in various energy storage and conversion applications.

MOF-derived three-dimensional porous dodecahedral structured bimetallic Mn/Co-C-N composite for high-performance durable oxygen reduction reaction electrocatalysts

Investigating high-efficiency oxygen reduction reaction (ORR) catalysts is one of the most effective methods for addressing the sluggish kinetics at the fuel cell cathode. Bimetallic three-dimensional porous materials have garnered significant attention due to their diverse structures, large specific surface area and synergistic catalytic effects. Herein, we synthesized a bimetallic three-dimensional porous dodecahedral structure, Mn/Co-C-N, derived from MOF using a straightforward approach. Experimental reults confirm that the strategic incorporation of Mn enhances the electrocatalytic activity for ORR. Meanwhile, the synergistic effects of Mn and Co, as well as the advantages of the dodecahedral structure for expediting electron transfer, all contribute to the exceptional ORR performance. Arc testing in an alkaline electrolyte reveals that the initial potential (Eonset) and the half-wave potential (E1/2) are 0.89 V and 0.80 V, closely approximating those of commercial Pt/C (20 wt%). Following 10 000 stability test cycles, the half-wave potential exhibits a mere 8 mV change, confirming its remarkable stability.

Prussian Blue-Derived Atomic Fe/Fe3C@N-Doped C Catalysts Supported by Carbon Cloth as Integrated Air Cathode for Flexible Zn-Air Batteries.

The development of an integrated air cathode with superior oxygen reduction reaction (ORR) performance is fundamental to flexible zinc-air batteries (ZABs) for wearable electronics. Herein, a self-assembled metal-organic framework (MOF)-derived strategy is proposed to prepare a atomic Fe/Fe3C@N-doped C catalysts supported by carbon cloth (CC) catalyst for use as an air cathode of flexible ZABs. The Prussian Blue precursor, which self-assembles on the surface of the carbon cloth due to electrostatic attraction, is critical in achieving the uniform dispersion of catalysts with high density loading on carbon cloth substrates. The hollow cubic structure, N-doped carbon layer coating, and the integrated electrode design can provide more accessible active sites and facilitate a rapid electron transfer and mass transport. Density functional theory (DFT) calculation reveals that the electronic interactions between the Fe-N4 and Fe3C dual active sites can optimize the adsorption-desorption behavior of oxygen intermediates formed during the ORR. Consequently, the Fe/Fe3C@N-doped C/CC exhibits an excellent half wave potential (E1/2 = 0.903V) and superior long-term cycling stability in alkaline environments. With excellent ORR performance, ZABs and flexible ZABs based on Fe/Fe3C@N-doped C/CC air cathode demonstrate excellent overall electrochemical performance in terms of open circuit voltage, maximum power density, flexibility, and cycling stability.

In Situ Construction of Perovskite Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ/CoRu Nanoparticles with Co-N-C Composite Enabling Efficient Bifunctional Electrocatalyst for Zinc-Air Batteries.

Bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential components of rechargeable zinc-air batteries. In this study, we synthesized a Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ (PBMCRO) perovskite composite with in situ exsolved CoRu nanoparticles and Co-N-C, functioning as an efficient bifunctional electrocatalyst for zinc-air batteries. The in situ exsolution of CoRu nanoparticles from the perovskite oxide was facilitated by the reducing action of 2-methylimidazole (2-MIM). Concurrently, Co-N-C was used to decorate PBMCRO, forming a novel bifunctional composite electrode of Co-N-C-PBMCRO. The incorporation of CoRu nanoparticles introduces a significant number of electrochemically active oxygen vacancies in the perovskite matrix, enhancing ORR and OER performance. Additionally, the Co-N-C synergistically improves electrochemical activity while preserving the structural stability of the perovskite oxide. The prepared Co-N-C-PBMCRO catalyst demonstrates significantly enhanced bifunctional performance compared to the undecorated pristine perovskite Pr0.5Ba0.5MnO3-δ (PBMO). The zinc-air battery with Co-N-C-PBMCRO catalyst achieve a peak power density of approximately 90 mW/cm2 and exhibit remarkable cycling stability for 788 h. This study presents a novel and effective strategy to enhance the catalytic performance of perovskite-based air electrodes for rechargeable metal-air batteries.

Two-Dimensional Covalent Organic Frameworks with Carbazole-Embedded Frameworks Facilitate Photocatalytic and Electrocatalytic Processes.

Catalytic technologies are pivotal in enhancing energy efficiency, promoting clean energy production, and reducing energy consumption in the chemical industry. The pursuit of novel catalysts for renewable energy is a long-term goal for researchers. In this work, we synthesized three two-dimensional covalent organic frameworks (COFs) featuring electron-rich carbazole-based architectures and evaluated their catalytic performance in photocatalytic organic reactions and electrocatalytic oxygen reduction reactions (ORRs). Pyrene-functionalized COF, termed as FCTD-TAPy, demonstrated excellent photocatalytic performance for amino oxidation coupling and showed a remarkable preference for substrates with electron-withdrawing groups (up to >99% Conv. and >99% Sel). Furthermore, FCTD-TAPy favored a four-electron transfer pathway during the ORR and exhibited favorable reaction kinetics (51.07 mV/dec) and a high turnover frequency (0.011 s-1). In contrast, the ORR of benzothiadiazole-based FCTD-TABT favored a two-electron transfer pathway, which exhibited a maximum double-layer capacitance of 14.26 mF cm-2, a Tafel slope of 53.01 mV/dec, and a hydrogen peroxide generation rate of 70.3 mmol g-1 h-1. This work underscores the potential of carbazole-based COFs as advanced catalytic materials and offers new insights into the design of metal-free COFs for enhanced catalytic performance.

FeCo Bimetallic ZIF Derivatives decorated with CoFe-LDH to Promote Bifunctional Oxygen Electrocatalysis Activation.

Reasonably screening the targeted oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) constituents and constructing high-efficiency and stabilized ORR/OER bifunctional electrocatalysts are pivotal for the advancement of rechargeable zinc-air batteries (ZABs). Here, CoFe layered double hydroxide (CoFe-LDH) nanosheets are deposited on nitrogen-doped graphite-carbon polyhedra with FeCo alloy nanoparticles (FeCo/LDH-NGCP). Due to the synergic effect between FeCo-NGCP, CoFe-LDH and FeCo/LDH-NGCP, the electrocatalyst with the abundant and accessible active sites can provide good charge/mass transfer, and thus shows wonderful ORR and OER bifunctional electrocatalytic performance. In ORR tests, FeCo/LDH-NGCP catalyst displays larger half-wave potential (E1/2, 0.89 V vs. 0.85 V), higher limiting current density (JL, 5.91 mA/cm2 vs. 5.14 mA/cm2) and better stability than commercial Pt/C. As for OER, FeCo/LDH-NGCP possesses a smaller overpotential (η) of 299.6 mV at a current density of 10 mA/cm2 and more durable stability than commercial RuO2 (330.6 mV). Furthermore, in ZAB tests, the cycling stability of ZAB-FeCo/LDH-NGCP (over 470 h) outperforms the ZAB-Pt/C+RuO2 (92 h) with commercial electrocatalyst (Pt/C+RuO2). Therefore, the FeCo/LDH-NGCP catalyst offers a new perspective to construct ZABs bifunctional catalysts and their commercial application in ZABs.

Boosting Zn-air battery performance: Fe single-atom anchored on F, N co-doped carbon nanosheets for efficient oxygen reduction

Sluggish oxygen reduction reaction (ORR) kinetics limit the development of metal-air batteries and fuel cells, hindering overall energy conversion efficiency. Therefore, significant research has focused on cost-effective, highly active, and exceptionally stable non-precious metal ORR electrocatalysts. This study presents the synthesis of a nanohybrid material called Fe SAs/FN-CNs. It is made up of single iron atoms embedded in ultrathin porous carbon nanosheets that are co-doped with F and N. The synthesis process involves an easy one-step pyrolysis technique without additional post-treatment. The Fe SAs/FN-CNs material is designed to function as an effective zinc-air battery ORR electrocatalyst. Based on their distinctive components and structure, the optimal Fe SAs/FN-CNs exhibit outstanding catalytic efficiency and long-lasting performance in the alkaline ORR. They have an onset potential (Eonset) of 0.95 V, a half-wave potential (E0.5) of 0.85 V, a kinetic current density (JK) of 20.49 mA cm−2 at 0.8 V, and a diffusion-limited current (Jd) of 6.2 mA cm−2. In addition, a Zn-air battery made using homemade Fe SAs/FN-CNs demonstrated a power density of 197 mW cm−2, a specific capacitance of 813.5 mAh g−1, and exceptional stability. It outperformed the commercial Pt/C by operating continuously for over 147 hours at 10 mA/cm² (discharge-charge). The Fe SAs/FN-CNs nanohybrid electrocatalyst shows great potential as an electrocatalyst for various metal-air batteries.

A Photo-Assisted Zinc-Air Battery with MoS2/Oxygen Vacancies Rich TiO2 Heterojunction Photocathode.

Converting solar energy into electrochemical energy is a sustainable strategy, but the design of photo-assisted zinc-air battery (ZAB) with efficient utilization of sunlight faces huge challenges. Herein, a photo-assisted ZAB of a three-electrode system using MoS2/oxygen vacancies-rich TiO2 heterojunction as charge cathode and Fe, N-doped carbon matrix (FeNC) as discharge cathode is constructed, where MoS2 is chosen as solar light-responsive catalytic material and TiO2 acts as electron transport layer and hole blocking layer, arising from a train of thought for efficient charging under sunlight irradiation and light-independent discharging. The introduction of oxygen vacancies in TiO2 facilitates the temporary trapping of carriers and triggers rapid carrier transfer at the interface of the heterojunction, which hinders the recombination of photogenerated holes, thereby facilitating their further participation in the oxygen evolution reaction. Moreover, FeNC exhibits superior oxygen reduction reaction performance due to strong d-π interactions. As a result, the well-built ZABs deliver a low charge voltage (0.71 V) under illumination at 0.1 mA cm-2, and a high power density (167.6mW cm-2) in dark. This work paves a special way for the development of ZABs by directly harvesting solar energy in charging and efficiently discharging regardless of lighting conditions.

Precise Construction of the Triple-Phase Boundary and Its Antiphosphate Poisoning Effect in the Confined Region.

As a critical component for the oxygen reduction reaction (ORR), platinum (Pt) catalysts exhibit promising catalytic performance in High-temperature-proton exchange membrane fuel cells (HT-PEMFCs). Despite their success, HT-PEMFCs primarily utilize phosphoric acid-doped polybenzimidazole (PA-PBI) as the proton exchange membrane, and the phosphoric acid within the PBI matrix tends to leach onto the Pt-based layers, easily causing toxicity. Herein, we first propose UiO-66@Pt3Co1-T composites with precisely engineered interfacial structures. The UiO-66@Pt3Co1-T exhibits an octahedral porous framework with uniform structural dimensions and even distribution of surface nanoparticles, which demonstrate superior ORR performance compared to commercial Pt/C. The unique structure and morphology of the composites also exhibit a favorable half-wave potential in different concentrations of phosphoric acid electrolyte, regulated by the phosphoric acid adsorption site and intensity.This finding suggests that the incorporation of Co could effectively modulate the Pt d-band center, thereby enhancing the ORR performance. Furthermore, the selective adsorption of phosphoric acid by ZrO2 enables precise control over the phosphoric acid distribution. Notably, the retention of the octahedral framework post high-temperature treatment facilitates the establishment of dual transport pathways for gases and protons, leading to a stable and efficient triple-phase boundary.

Bismuth Nanoparticles and Single Iron Atoms on Carbon Derived from a Covalent Organic Framework Synergistically Catalyze the Oxygen Reduction Reaction.

The utilization of catalysts comprising metal nanoparticle has been beneficial for enhancing the performance of oxygen reduction reaction (ORR). However, the inadequate intrinsic activity of these catalysts still presents a significant challenge, limiting their overall effectiveness. This issue can be addressed by introducing single atoms, which can create a synergistic effect with the nanoparticles to catalyse and thereby improve performance. Nevertheless, the synergistic catalysis of nanoparticles and single atoms is still under investigation. In this study, we fabricated a core-shell structured carbon framework incorporating Fe single atoms and Bi nanoparticles through the pyrolysis of COF and MOF core-shell structures. Introducing Fe single atoms into ZIF-8, with Fe-ZIF-8 as the core and Bi-containing COF as the shell, resulted in higher ORR activity. The catalyst exhibited a half-wave potential of 0.867 V and a high current density of 6.68 mA cm-2 in 0.1 M KOH, which were comparable to those of Pt/C equivalent. This study provides new research concepts for exploring the application of single atoms and nanoparticles in catalytic oxygen reduction reactions through synergistic effects.

Optimizing Activity and Stability in AgCl‐CuO Electrocatalysts: Insights from Different Morphologies for Enhanced ORR Performance

Highly enduring and methanol‐tolerant electrocatalysts are pertinent to revolutionizing direct methanol fuel cell (DMFC) technologies. Transition metal‐based electrocatalysts are anticipated to rank among the remarkable electrocatalysts for boosting the sluggish Oxygen Reduction Reaction (ORR) kinetics. Herein, we report a facile approach to optimize the activity and stability of the AgCl‐CuO systems. The tailored Nano Particle‐Nano Rod (NP‐NR) and Nano Leaf (NL) like morphologies deliver remarkable bifunctional catalytic performance for oxygen reduction and hydrogen evolution reactions, sustained activity, and comparatively better stability for ORR. A meager shift of only 0.014 V and 0.024 V in the half‐wave potential is observed in the NP‐NR and NL structures, respectively, for the ORR even after 2500 cycles. Furthermore, both the AgCl‐CuO composite exhibits an excellent tolerance to methanol.