Air Cathode Catalyst Research Articles

Preparation and Electrocatalytic Properties of One-Dimensional Nanorod-Shaped N, S Co-Doped Bimetallic Catalysts of FeCuS-N-C

Metal air batteries have gradually attracted public attention due to their advantages such as high power density, high energy density, high energy conversion efficiency, and clean and green products. Reasonable design of oxygen reduction reaction (ORR) catalysts with high cost-effectiveness, high activity, and high stability is of great significance. Metal organic frameworks (MOFs) have the advantages of large specific surface area, high porosity, and designability, which make them widely used in many fields, especially in catalysis. This paper starts with regulating and optimizing the composition and structure of MOFs. A series of N, S co-doped electrocatalysts FeCuS-N-C were prepared by two high-temperature pyrolysis processes using N-doped carbon hollow nanorods derived from ZIF-8 as the substrate. The one-dimensional nanorod material derived from this MOF exhibits excellent electrocatalytic ORR performance (Eonset = 0.998 V, E1/2 = 0.874 V). When used as the air cathode catalyst for zinc air batteries and assembled into liquid ZABs, the battery discharge curve was calculated and found to have a maximum power density of 142.7 mW cm−2, a specific capacity of 817.1 mAh gZn−1, and a cycling stability test of over 400 h. This study provides an innovative approach for designing and optimizing non-precious metal catalysts for zinc air batteries.

Main-group element-boosted oxygen electrocatalysis of Cu-N-C sites for zinc-air battery with cycling over 5000 h

Developing highly active and durable air cathode catalysts is crucial yet challenging for rechargeable zinc-air batteries. Herein, a size-adjustable, flexible, and self-standing carbon membrane catalyst encapsulating adjacent Cu/Na dual-atom sites is prepared using a solution blow spinning technique combined with a pyrolysis strategy. The intrinsic activity of the Cu-N4 site is boosted by the neighboring Na-containing functional group, which enhances O2 adsorption and optimizes the rate-determining step of O2 activation (*O2 → *OOH) during the oxygen reduction reaction process. Meanwhile, the Cu-N4 sites are encapsulated within carbon nanofibers and anchored by the carbon matrix to form a C2-Cu-N4 configuration, thereby reinforcing the stability of the Cu centers. Moreover, the introduction of Na-containing functional groups on the carbon atoms significantly reduces the positive charge on their outer shell C atoms, rendering the carbon skeletons less susceptible to corrosion by oxygen species and further preventing the dissolution of Cu centers. Under these multi-type regulations, the zinc-air battery with Cu/Na-carbon membrane catalyst as the air cathode demonstrates long-term discharge/charge cycle stability of over 5000 h. This considerable stability improvement represents a critical step towards developing Cu-N4 active sites modified with the neighboring main-group metal-containing functional groups to overcome the durability barriers of zinc-air batteries for future practical applications.

Accordion-like multilayered titanium nitride enables FeN4-O axial coordination of iron phthalocyanine as efficient catalysts for oxygen reduction reaction

The susceptibility of MXenes to oxidation leads to rapid chemical degradation and functional loss, and hence limits their diverse applications. In this study, we develop a scalable strategy to transform blocky, condensed titanium nitride (TiN) into accordion-like leafy titanium nitride (M-TiN), which exhibits enhanced chemical stability and an increased surface area. When functionalized with iron phthalocyanine (FePc), the resulting M-TiN/FePc composite displays a remarkable electrocatalytic activity towards the oxygen reduction reaction (ORR) due to the formation of FeN4-O axial coordination and a low-to-intermediate Fe spin state, as confirmed by spectroscopy and magnetic measurements. This leads to electron filling in the antibonding orbitals composed of Fe 3dz2 and O2 π* orbitals, significantly improving O2 activation and ORR activity. Significantly, with the M-TiN/FePc composite as the air cathode catalyst, a zinc-air battery achieves a superior power density of 270.31 mW cm−2 and enhanced cyclability compared to that with commercial Pt/C. Results from this study highlight the significance of morphological engineering of TiN in regulating the atomic configuration of adsorbed metal active centers and hence their catalytic activity, in particular, in harsh oxidative conditions.

Fluorine and sulfur atoms induced N-doped 3D porous carbon catalyzing oxygen reduction in the zinc-air battery

Introducing other heteroatom is considered to be a highly effective approach to improve the limited catalytic activity from single nitrogen element doping in nitrogen-doped porous carbon materials. In this work, F and S-modified nitrogen-doped porous carbon (F-S-N-C) is prepared by annealing the assembly material of poly3-fluoro aniline, hydroxyethyl sulfonic acid and g-C3N4, in which the g-C3N4 is employed as template agent and pore-forming agent. A series of characterization techniques indicate that simultaneous doping of F and the S atoms enhance the electron transfer and construct more defects for N-doped 3D porous carbon, resulting in improved electrocatalytic performance. The prepared F and S-cooperated nitrogen-doped porous carbon (F-S-N-C) exhibits significantly improved oxygen reduction reaction electrocatalytic activity in alkaline media with a half-wave potential of 0.808 V. The zinc-air battery (ZAB) with F-S-N-C as the air cathode catalyst demonstrates a peak power density of 167 mW cm−2, which is higher than that of commercial Pt/C (158 mW cm−2). Moreover, the specific capacity of the F-S-N-C-based ZAB reaches to 817 mAh·g−1.

Ar/NH3 Plasma Etching of Cobalt-Nickel Selenide Microspheres Rich in Selenium Vacancies Wrapped with Nitrogen Doped Carbon Nanotubes as Highly Efficient Air Cathode Catalysts for Zinc-Air Batteries.

This work utilizes defect engineering, heterostructure, pyridine N-doping, and carbon supporting to enhance cobalt-nickel selenide microspheres' performance in the oxygen electrode reaction. Specifically, microspheres mainly composed of CoNiSe2 and Co9Se8 heterojunction rich in selenium vacancies (VSe·) wrapped with nitrogen-doped carbon nanotubes (p-CoNiSe/NCNT@CC) are prepared by Ar/NH3 radio frequency plasma etching technique. The synthesized p-CoNiSe/NCNT@CC shows high oxygen reduction reaction (ORR) performance (half-wave potential (E1/2) = 0.878V and limiting current density (JL) = 21.88mA cm-2). The JL exceeds the 20wt% Pt/C (19.34mA cm-2) and the E1/2 is close to the 20wt% Pt/C (0.881V). It also possesses excellent oxygen evolution reaction (OER) performance (overpotential of 324 mV@10mA cm-2), which even exceeds that of the commercial RuO2 (427 mV@10mA cm-2). The density functional theorycalculation indicates that the enhancement of ORR performance is attributed to the synergistic effect of plasma-induced VSe· and the CoNiSe2-Co9Se8 heterojunction. The p-CoNiSe/NCNT@CC electrode assembled Zinc-air batteries (ZABs) show a peak power density of 138.29mW cm-2, outperforming the 20wt% Pt/C+RuO2 (73.9mW cm-2) and other recently reported catalysts. Furthermore, all-solid-state ZAB delivers a high peak power density of 64.83mW cm-2 and ultra-robust cycling stability even under bending.

Co-doped hollow nanospheres with low Pt loading for electrocatalytic oxygen reduction and zinc-air batteries

Preparing high-performance catalysts for oxygen reduction reaction (ORR) with low Pt loading is crucial to promote the development of clean energy storage devices such as metal air batteries. Herein, Co/N-HCMs support material with isolated Co atoms and hollow flower-like structure could be prepared by a self-sacrificing template strategy. Co/N-HCMs are then used to anchor Pt to obtain PtCo/N-HCMs catalyst with low Pt loading. Thanks to its improved specific surface area, hierarchical porous structure, and reinforced metal-support interactions, the obtained PtCo/N-HCMs deliver high onset potential of 0.99 V and half-wave potential of 0.82 V, and an excellent durability. When used as air cathode catalyst, PtCo/N-HCMs-based Zinc-air battery (ZAB) exhibits a power density of up to 202 mW cm−2, which is significantly better than ZAB assembled with commercial Pt/C. This study provides an effective strategy for preparing high-performance electrocatalysts with low precious metal content for use as the cathode of metal-air batteries.

Multifunctional carbon armor: Synchronously improving oxygen reaction kinetics, mass transfer dynamics, and robustness of transition metal alloy based hybrid catalyst

Construction of robust protective cover on delicate active sites is a frequently-used scheme to enhance the durability of air-cathode catalyst working in harsh environment, thus the lifespan of rechargeable Zinc-air batteries (ZABs). Paradoxically, this would degrade the activity due to the constricted accessibility of active sites to reactants. Herein, carbon nanotubes with abundant mesoporous defects and Fe-N4 species were elaborately designed to be multifunctional protective armor to encapsulate Ni3Fe nano-alloys (Ni3Fe@CNTs/Fe-N4) for bifunctional oxygen electrocatalyst. In/ex-situ spectroscopy analysis and theoretical calculations reveal that the constructed mesoporous carbon defects effectively facilitate the multiphase mass transfer and the oxygen evolution reaction kinetics via strong electrons coupling with packaged Ni3Fe nano-alloys. Meanwhile, the synchronously introduced Fe-N4 moieties could serve as oxygen reduction active sites. Thus, the obtained Ni3Fe@CNTs/Fe-N4 hybrid electrocatalyst simultaneously exhibits remarkable bifunctional catalytic activity (E1/2=0.86/Ej=10=1.59 V vs RHE) and durability over 450 h in the chronoamperometric test at 1.59 V, endowing the assembled Zn-air batteries (ZABs) with a high power density (150 mW cm−2) and lifespan (307 h), much better than that employing benchmark Pt/C+RuO2 mixed catalyst. This work demonstrates an innovative design route for the multifunctional armor to concurrently enhance the durability, activity and robustness of air-cathode-catalyst for ZABs.

An Innovative Approach to Assess the Potentiality of Using Activated Carbon and Rice Husk Ash in Aluminum-Air Battery

Aluminum-air (Al-air) cells have the potential to become vital in energy storage applications in the future because of their high energy density, which is even higher than that of commonly used lithium-ion batteries. However, it is not used widely because the cost of air cathode catalysts and metal anode is high. However, suppose the catalysts are replaced with activated carbon or rice husk ash as an alternative and recycled aluminum foil as an anode. In that case, the production cost might be feasible for the vast use of this type of cell. This study's main objective is to utilize some commonly available material in fabricating an Al-air battery suitable for small and day-to-day usage, reducing production costs and limitations. In this paper, a focused analysis was made on the feasibility of using an activated carbon and rice husk mixture as an air cathode catalyst for an Al-air cell, and the observations were interesting. About 11 samples of a mixture of rice husk ash (RHA) and activated carbon (AC) in different ratios have been made to find the best results from 0.68-0.72 V, which increases by 8-20%, measuring each sample after 3 days. In this study, another attempt was made to replace the graphite cathode of a dry cell with a mixture of AC and RHA. Voltage drop is quite negligible for the mixture of 10% RHA. The resulting voltage is similar to the new 100% activated carbon battery as a cathode. If considering the environmental effect, using recycled activated carbon and rice husk ash will decrease pollution and open a new door to apply in primary cells.

Low-Overpotential Rechargeable Na-CO2 Batteries Enabled by an Oxygen-Vacancy-Rich Cobalt Oxide Catalyst.

Rechargeable sodium-carbon dioxide (Na-CO2) batteries have been proposed as a promising CO2 utilization technique, which could realize CO2 reduction and generate electricity at the same time. They suffer, however, from several daunting problems, including sluggish CO2 reduction and evolution kinetics, large polarization, and poor cycling stability. In this study, a rambutan-like Co3O4 hollow sphere catalyst with abundant oxygen vacancies was synthesized and employed as an air cathode for Na-CO2 batteries. Density functional theory calculations reveal that the abundant oxygen vacancies on Co3O4 possess superior CO2 binding capability, accelerating CO2 electroreduction, and thereby improving the discharge capacity. In addition, the oxygen vacancies also contribute to decrease the CO2 decomposition free energy barrier, which is beneficial for reducing the overpotential further and improving round-trip efficiency. Benefiting from the excellent catalytic ability of rambutan-like Co3O4 hollow spheres with abundant oxygen vacancies, the fabricated Na-CO2 batteries exhibit extraordinary electrochemical performance with a large discharge capacity of 8371.3 mA h g-1, a small overpotential of 1.53 V at a current density of 50 mA g-1, and good cycling stability over 85 cycles. These results provide new insights into the rational design of air cathode catalysts to accelerate practical applications of rechargeable Na-CO2 batteries and potentially Na-air batteries.

Preparation of Co[sbnd]N co-doped carbon nanosheets electrocatalyst for efficient oxygen reduction reaction in zinc-air battery

It is very vital that there be a high-activity and serviceable catalyst for the oxygen reduction reaction (ORR) in the Zn-air Battery. Herein, utilizing g-C3N4 as a self-sacrifice template and Cobalt-His framework as the precursor, a simple strategy was developed to synthesize Co/N co-doped carbon nanosheets (CoNC 800) as a metal electrocatalyst for ORR. Due to the Co/N co-doped CoNX site and large specific surface area, the acquired materials show a preeminent ORR catalytic activity with an initial potential (~0.96 V) and half-wave potential (E1/2) of 0.85 V (vs. RHE) in an alkaline medium. Most importantly, the material has superior long-term stability and methanol tolerance than Pt/C. Furthermore, we assembled the Zn-air battery employing catalyst as an air cathode catalyst, demonstrating maximum power densities of 144 mWcm−2, a specific capacity of 821.50 Wh·kg−1, and charge/discharge cycle stability of more than 140 h. The nanosheet structure electrocatalysts derived from the Cobalt-His framework and g-C3N4 provide an innovative and instructive approach to the design of diverse nanomaterials.

Regulating the frontier orbital of iron phthalocyanine with nitrogen doped carbon nanosheets for improving oxygen reduction activity.

Iron phthalocyanine (FePc) has attracted widespread attention for its tunable electronic structure. However, the Fe-N sites suffer from undesirable oxygen reduction activity due to the symmetric geometries. A suitable substrate was thus needed to induce electron redistribution around Fe-N to improve the activity. Herein, ultrathin nitrogen-doped carbon nanosheets (N-CNSs) were prepared by a simple high temperature pyrolysis. Then iron phthalocyanine was loaded on the ultrathin nitrogen-doped carbon nanosheets (FePc@N-CNSs) by a low-cost and simple solution method. This composite catalyst shows an excellent ORR activity with a half potential of 0.88 V, an onset potential of 0.99 V and durability superior to commercial Pt/C. When used as an air cathode catalyst for rechargeable zinc-air batteries, FePc@N-CNS modified batteries outperform Pt/C + RuO2 modified batteries with higher power density and superior constant current charge-discharge cycling stability of 37 hours. The regulated electronic structure of FePc by the N-CNS substrate was revealed further by DFT calculations, which explained the enhanced adsorption of the active center to the intermediates and the increased ORR performance.

Supporting Critical Raw Material Circularity – Graphite from Waste LIBS to Zn-Air Batteries

The use of Li-ion batteries (LIBs) in electrical vehicles and consumer electronics is continuously on the rise which means that the amount of spent LIB (SLIB) is on the rise as well. The sustainable recycling of SLIB for production of secondary resources will prevent the loss of valuable materials and ensures safe and economical management of used batteries. During industrial black mass recycling process only Co and Ni from SLIBs is currently recycled, though LIBs contain many other valuable materials too. Graphite, which is used as an anode active material in LIBs, is discarded as a waste during industrial recycling process. Repurposing inexpensive waste graphite has a huge potential to be alternative for pristine graphite.In this research a novel way to prepare bifunctional oxygen electrocatalyst from industrially produced and hydrometallurgically leached black mass leach residue is shown. The recycling leach residue is utilized as a valuable raw material, graphite and transition metal (Co, Mn, Ni) source, with N-precursor for the synthesis of N-Me-C graphite-based electrocatalyst. For the first time the battery metal residues, left into SLIBs recycling waste, are strategically exploited to achieve metal co-doping of graphite-based material. Battery derived electrocatalysts demonstrated promising electrocatalytic activity towards ORR and OER in alkaline media. Moreover, the novel bifunctional oxygen electrocatalysts were used in a rechargeable Zn-air battery as an air cathode catalyst and achieved a high-power density of 104 mW·cm-2 (Figure 1). The advantageous electrochemical activity of the catalyst materials was linked with its surface morphology, structure, porosity, and elemental composition.This research shows the great potential of SLIBs black mass leach residue as a resource for the more sustainable production of high performance and low-cost bifunctional oxygen electrocatalyst appliable in Zn-air battery. Figure 1

Nitrogen-Doped Carbon Cubosomes as an Efficient Electrocatalyst with High Accessibility of Internal Active Sites.

Porous carbon particles (PCPs) present considerable potential for applications across a wide range of fields, particularly within the realms of energy and catalysis. The control of their overall morphologies and pore structures has remained a big challenge. Here, using metal-organic frameworks (MOFs) as the precursor and polymer cubosomes (PCs) as the template, nitrogen-doped carbon cubosomes (SP-NCs) with a single primitive bicontinuous architecture are prepared. SP-NCs inherit the high porosity of MOFs, generating a high specific surface area of 825 m2 g-1 and uniformly distributed active sites with a 5.9 at % nitrogen content. Thanks to the presence of three-dimensional continuous mesochannels that enable much higher accessibility of internal active sites over those of their porous counterparts' lack of continuous channels, SP-NCs exhibit superior electrocatalytic performance for oxygen reduction reaction with a half-wave potential of 0.87 V, situating them in the leading level of the reported carbon electrocatalysts. Serving as an air cathode catalyst of the Zn-air battery, SP-NCs exhibit excellent performance, outperforming the commercial Pt/C catalysts.

Synergistic effects of hierarchical porous structures and ultra-high pyridine nitrogen doping enhance the oxygen reduction reaction electrocatalytic performance of metal-free laminated lignin-based carbon

Construction of non-metallic biomass-carbon based catalysts for fuel cell air cathode applications has attracted great attention in recent years. In this work, a convenient and clean technique was developed to fabrication nitrogen-doped lignin-based hierarchical porous lamellar carbon (N-LHPC) via lignin as the carbon precursor, melamine/urea as the nitrogen source and ZnC2O4.2H2O as the chemical activator. The N-LHPC has a high specific surface area (491.5 m2 g−1) and macroporous/mesoporous/microporous structures. The nitrogen doping of N-LHPC can reach 16.37 wt%, with a high pyridinic nitrogen content of 41.39 at.%. N-LHPC exhibits a high half-wave potential (0.87 V) and a large limiting current density (5.75 mA cm−2) in 0.1 mol KOH media which is comparable to the commercial Pt/C catalysts. Furthermore, N-LHPC was assembled as air cathode catalyst for Zn-air batteries to evaluate its practical catalytic performance, and the power density was as high as 191 mW cm−2, which was superior to the 20 wt% Pt/C electrocatalyst. This research demonstrates that lignin is a promising carbon source for the fabrication of high catalytic activity and economical electrocatalysts for energy storage systems.

Ultra-fine Fe3C nanoparticles decorated in the Fe–N co-doped carbon networks with hierarchical nanoarchitectonics towards efficient oxygen reduction electrocatalysis

The iron-nitrogen co-doped carbon (Fe–N–C) materials have considered one of the oxygen reduction reaction catalysts with the best potential. Unfortunately, their insufficient intrinsic activity and low active sites result in thick cathode catalytic layers of fuel cell, which has limited discharge performance of the Fe–N–C catalysts in the fuel cells. Herein, a supramolecular assembly strategy is designed to prepare accessible Fe-Nx sites and ultra-fine Fe3C nanoparticles in porous carbon nanosheet with optimized pore structure toward oxygen reduction electrocatalysis. It is found that supramolecular assembly strategy has significantly increased the specific surface area and Fe-Nx site content, and induced the formation of highly dispersed Fe3C nanoparticles, which contributes to the high electrochemical active surface area and catalytic activity. The obtained FeNC-900-S catalyst exhibits a high half-wave potential of 0.860 V and a current density of up to 8.28 mA/cm2 (Jk at 0.85 V) in 0.1 M KOH, outperforming the those of commercial Pt/C. More importantly, when the FeNC-900-S is employed as an air cathode catalyst towards zinc-air batteries, it obtains an open-circuit voltage of 1.548 V, a power density of 188.8 mW/cm2 and a specific capacity of 790.5 mAh/g.

Adjustable antiperovskite ZnCCe3−xNix/CNFs as an efficient bifunctional Zn-air batteries electrocatalyst

The development of efficient, stable and low-cost dual-function electrocatalysts and applicated it to Zn-air batteries are very important for the development of renewable energy storage and conversion technologies. Antiperovskite catalysts have attracted much attention recently due to their advantages of adjustable structure and high element selectivity. In this work, a flexible and adjustable antiperovskite catalyst ZnCCe3−xNix (0 ≤ x ≤ 3) loaded on carbon fiber (ZnCCe3−xNix/CNFs) was prepared by electrospinning technology and used as an air cathode catalyst for rechargeable Zn-air batteries. By doping the X-site with highly conductive transition metal Ni, the electronic structure of the catalyst ZnCCe3−xNix/CNFs was optimized, and the catalytic activity of the antiperovskite bimetallic X-site was tuned to achieve an efficient and synergistic catalytic reaction. Among them, ZnCCe2.7Ni0.3/CNFs showed excellent OER/ORR bi-functional catalytic activity (ΔE = 0.82 V) and good stability. When ZnCCe2.7Ni0.3/CNFs is used as the cathode catalyst for rechargeable Zn-air batteries, it shows a power density of 117.99 mW cm−2, and the cycle stability can be maintained for up to 300 h, indicating its application potential in the field of Zn-air batteries.

Low-Potential Iodide Oxidation Enables Dual-Atom CoFe─N─C Catalysts for Ultra-Stable and High-Energy-Efficiency Zn-Air Batteries.

The low energy efficiency and limited cycling life of rechargeable Zn-air batteries (ZABs) arising from the sluggish oxygen reduction/evolution reactions (ORR/OERs) severely hinder their commercial deployment. Herein, a zeolitic imidazolate framework (ZIF)-derived strategy associated with subsequent thermal fixing treatment is proposed to fabricate dual-atom CoFe─N─C nanorods (Co1 Fe1 ─N─C NRs) containing atomically dispersed bimetallic Co/Fe sites, which can promote the energy efficiency and cyclability of ZABs simultaneously by introducing the low-potential oxidation redox reactions. Compared to the mono-metallic nanorods, Co1 Fe1 ─N─C NRs exhibit remarkable ORR performance including a positive half-wave potential of 0.933V versus reversible hydrogen electrode (RHE) in alkaline electrolyte. Surprisingly, after introducing the potassium iodide (KI) additive, the oxidation overpotential of Co1 Fe1 ─N─C NRs to reach 10mAcm-2 can be significantly reduced by 395mV compared to the conventional destructive OER. Theoretical calculations show that the markedly decreased overpotential of iodide oxidation can be ascribed to the synergistic effects of neighboring Co─Fe diatomic sites as the unique adsorption sites. Overall, aqueous ZABs assembled with Co1 Fe1 ─N─C NRs and KI as the air-cathode catalyst and electrolyte additive, respectively, can deliver a low charging voltage of 1.76V and ultralong cycling stability of over 230h with a high energy efficiency of ≈68%.

Formulating N-Doped Carbon Hollow Nanospheres with Highly Accessible Through-Pores to Isolate Fe Single-Atoms for Efficient Oxygen Reduction.

It is challenging yet promising to design highly accessible N-doped carbon skeletons to fully expose the active sites inside single-atom catalysts. Herein, mesoporous N-doped carbon hollow spheres with regulatable through-pore size can be formulated by a simple sequential synthesis procedure, in which the condensed SiO2 is acted as removable dual-templates to produce both hollow interiors and through-pores, meanwhile, the co-condensed polydopamine shell is served as N-doped carbon precursor. After that, Fe─N─C hollow spheres (HSs) with highly accessible active sites can be obtained after rationally implanting Fe single-atoms. Microstructural analysis and X-ray absorption fine structure analysis reveal that high-density Fe─N4 active sites together with tiny Fe clusters are uniformly distributed on the mesoporous carbon skeleton with abundant through-pores. Benefitted from the highly accessible Fe─N4 active sites arising from the unique through-pore architecture, the Fe─N─C HSs demonstrate excellent oxygen reduction reaction (ORR) performance in alkaline media with a half-wave potential up to 0.90V versus RHE and remarkable stability, both exceeding the commercial Pt/C. When employing Fe─N─C HSs as the air-cathode catalysts, the assembled Zn-air batteries deliver a high peak power density of 204mWcm-2 and stable discharging voltage plateau over 140h.

Precise Modulation of Carbon Activity Sites in Metal-Free Covalent Organic Frameworks for Enhanced Oxygen Reduction Electrocatalysis.

Metal-free carbon-based materials have gained recognition as potential electrocatalysts for the oxygen reduction reaction (ORR) in new environmentally-friendly electrochemical energy conversion technologies. The presence of effective active centers is crucial for achieving productive ORR. In this study, we present the synthesis of two metal-free dibenzo[a,c]phenazine-based covalent organic frameworks (DBP-COFs), specifically JUC-650 and JUC-651, which serve as ORR electrocatalysts. Among them, JUC-650 demonstrates exceptional catalytic performance for ORR in alkaline electrolytes, exhibiting an onset potential of 0.90V versus RHE and a half-wave potential of 0.72V versus RHE. Consequently, JUC-650 stands out as one of the most outstanding metal-free COF-based ORR electrocatalysts report to date. Experimental investigations and density functional theory calculations confirm that modulation of the frameworks' electronic configuration allows for the reduction of adsorption energy at the Schiff-base carbon active sites, leading to more efficient ORR processes. Moreover, the DBP-COFs can be assembled as excellent air cathode catalysts for zinc-air batteries (ZAB), rivaling the performance of commercial Pt/C. This study provides valuable insights for the development of efficient metal-free organoelectrocatalysts through precise regulation of active site strategies.

Fe-Fe3N composite nitrogen-doped carbon framework: Multi-dimensional cross-linked structure boosting performance for the oxygen reduction reaction electrocatalysis and zinc-air batteries

Taking into consideration the sluggish kinetics of the oxygen reduction reaction (ORR) and the distinct three-phase environment of the electrode, it is crucial to optimize the surface structure of the electrocatalyst. This study employs a sol–gel approach to synthesize a Fe-Fe3N composite three-dimensional nitrogen-doped carbon framework (Fe-Fe3N/3DNC) and utilize it as the electrocatalyst for a zinc-air battery. The material possesses a multi-dimensional cross-linking frame structure comprised of one-dimensional and two-dimensional crosslinks, which effectively reduce the diffusion mean-free path of oxygen. Moreover, the iron–nitrogen site and nitrogen-rich carbon substrate both exhibit exceptional electrocatalytic activity for ORR. Consequently, a conventional liquid zinc-air battery utilizing this material as the air cathode catalyst exhibits a maximum power density of 242.8 mW cm−2, surpassing that of commercial Pt/C. Additionally, DFT calculations further confirm the crucial enhancing influence of Fe3N in the Fe-Fe3N/3DNC composite on ORR. This research provides valuable insights for the development of ORR electrocatalysts with outstanding efficiency.