Boosted electrocatalytic activity and durability of CuFe/NC by modulating the interfacial composition and electronic structure for efficient oxygen reduction reaction.

Oxygen reduction reaction (ORR) serves as the foundation for various electrochemical energy storage devices. Fe/NC catalysts are expected to replace commercial Pt/C as oxygen electrode catalysts based on the structural tunability at the atomic level, abundant iron ore reserves and excellent activity. Nevertheless, the lack of durability and low active site density impede its advancement. In this work, a durable catalyst, CuFe/NC, for ORR was prepared by modulating the interfacial composition and electronic structure. The introduction of Cu nanoclusters partially eliminates the Fenton effect from Fe and optimizes the electron structure of FeNx, thereby effectively enhancing the long-term durability and activity. The prepared CuFe/NC exhibits a half-wave potential (E1/2) of 0.90 V and superior stability with a decrease in E1/2 of only 20 mV after 10,000 cycles. The assembled alkaline Zinc-Air batteries (ZABs) with CuFe/NC exhibit an open-circuit potential of 1.458 V. At a current density of 5 mA cm-2, the batteries are capable of operation for 600 h with a stable polarization. This CuFe/NC may promote the practical application of novel and renewable electrochemical energy storage devices.

MOF-on-MOF-derived FeCo@NC OER&ORR bifunctional electrocatalysts for zinc-air batteries.

Zinc-air batteries, as one of the emerging areas of interest in the quest for sustainable energy solutions, are hampered by the intrinsically sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and still suffer from the issues of low energy density. Herein, we report a MOF-on-MOF-derived electrocatalyst, FeCo@NC-II, designed to efficiently catalyze both ORR (Ehalf = 0.907 V) and OER (Ej=10 = 1.551 V) within alkaline environments, surpassing esteemed noble metal benchmarks (Pt/C and RuO2). Systematically characterizations and density functional theory (DFT) calculations reveal that the synergistic effect of iron and cobalt bimetallic and the optimized distribution of nitrogen configuration improved the charge distribution of the catalysts, which in turn optimized the adsorption / desorption of oxygenated intermediates accelerating the reaction kinetics. While the unique leaf-like core-shell morphology and excellent pore structure of the FeCo@NC-II catalyst caused the improvement of mass transfer efficiency, electrical conductivity and stability. The core and shell of the precursor constructed through the MOF-on-MOF strategy achieved the effect of 1 + 1 > 2 in mutual cooperation. Further application to zinc-air batteries (ZABs) yielded remarkable power density (212.4 mW/cm2), long cycle (more than 150 h) stability and superior energy density (∼1060 Wh/kg Zn). This work provides a methodology and an idea for the design, synthesis and optimization of advanced bifunctional electrocatalysts.

Encapsulating CoNi nanoparticles into nitrogen-doped carbon nanotube arrays as bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries.

The high theoretical specific energy and environmental friendliness of zinc-air batteries (ZABs) have garnered significant attention. However, the practical application of ZABs requires overcoming the sluggish kinetics associated with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, 3D self-supported nitrogen-doped carbon nanotubes (N-CNTs) arrays encapsulated by CoNi nanoparticles on carbon fiber cloth (CoNi@N-CNTs/CFC) are synthesized as bifunctional catalysts for OER and ORR. The 3D interconnected N-CNTs arrays not only improve the electrical conductivity, the permeation and gas escape capabilities of the electrode, but also enhance the corrosion resistance of CoNi metals. DFT calculations reveal that the co-existence of Co and Ni synergistically reduces the energy barrier for OOH conversion to OH, thereby optimizing the Gibbs free energy of the catalysts. Additionally, analysis of the change in energy barrier during the rate-determining step suggests that the primary catalytic active center is Ni site for OER. As a result, CoNi@N-CNTs/CFC exhibits superior catalytic activity with an overpotential of 240 mV at 10 mA cm-2 toward OER, and the onset potential of 0.92 V for ORR. Moreover, utilization of CoNi@N-CNTs/CFC in liquid and solid-state ZABs exhibited exceptional stability, manifesting a consistent cycling operation lasting for 100 and 15 h, respectively.

Co2P/CoP embedded in N, P, S triply-doped hollow carbon towards enhanced oxygen electrocatalysis.

Simultaneously dispersing phosphide crystallites and multiple heteroatoms in hollow carbon is a significant yet challenging task for achieving high-performance oxygen electrocatalysts of zinc-air batteries. Herein, a simple wrapping-pyrolysis strategy is proposed to prepare Co2P/CoP embedded in N, P, S triply-doped hollow carbon (Co2P/CoP@NPS-HC). Co2P/CoP@NPS-HC composite features hollow polyhedral structure populated with numerous catalytically active Co2P/CoP nanoparticles and N, P, S heteroatoms. This optimized catalyst exhibits excellent activity for oxygen reduction reaction, with a half-wave potential of 0.82 V vs. RHE, and impressive enhancement for oxygen evolution reaction, indicated by an overpotential of 400 mV at 10 mA cm-2. Moreover, Co2P/CoP@NPS-HC catalyst exhibits greater durability and superior methanol tolerance compared to commercial Pt/C. The excellent bifunctional electrocatalytic performance of Co2P/CoP@NPS-HC catalyst is attributed to the synergistic effect of uniformly dispersed Co2P/CoP nanoparticles and N, P, S triply-doped hollow carbon structure. The former provides abundant catalytically active sites, while the latter offers a high accessible specific surface area, as well as enhances catalytic activity and electronic conductivity due to its altered charge distribution.

Enhanced oxygen evolution and power density of Co/Zn@NC@MWCNTs for the application of zinc-air batteries.

Rechargeable zinc-air batteries (ZABs) are viewed as a promising solution for electric vehicles due to their potential to provide a clean, cost-effective, and sustainable energy storage system for the next generation. Nevertheless, sluggish kinetics of the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR) at the air electrode, and low power density are significant challenges that hinder the practical application of ZABs. The key to resolving the development of ZABs is developing an affordable, efficient, and stable catalyst with bifunctional catalytic. In this study, we present a series of bifunctional catalysts composed of Co/Zn nanoparticles uniformly embedded in nitrogen-doped carbon (NC) and multi-walled carbon nanotubes (MWCNTs) denoted as Co/Zn@NC@MWCNTs. The incorporation of MWCNTs using a facile and non-toxic method significantly decreased the overpotential of the OER from 570 to 430 mV at 10 mA cm-2 and the peak power density from 226 to 263 mW cm-2. Besides, the electrochemical surface area measurements and electrochemical impedance spectroscopy indicate that the three-dimensional (3D) network structure of MWCNTs facilitates mass transport for ORR and reduces electron transfer resistance during OER, leading to a small potential gap of 0.86 V between OER and ORR, high electron transfer number (3.92-3.98) of the ORR, and lowest Tafel slope (47.8 mV dec-1) of the OER in aqueous ZABs. In addition, in-situ Raman spectroscopy revealed a notable decrease in the ID/IG ratio for the optimally configured Co/Zn@NC@MWCNTs (75:25), indicating a reduction in defect density and improved structural ordering during the electrochemical process, which directly contributes to enhanced ORR activity. Hence, this study provides an excellent strategy for constructing a bifunctional catalyst material with a 3D MWCNTs conductive network for the development of advanced ZAB systems for sustainable energy applications.

Copper dual-doping strategy of porous carbon nanofibers and nickel fluoride nanorods as bi-functional oxygen electrocatalysis for effective zinc-air batteries.

Designing and developing efficient, low-cost bi-functional oxygen electrocatalysts is essential for effective zinc-air batteries. In this study, we propose a copper dual-doping strategy, which involves doping both porous carbon nanofibers (PCNFs) and nickel fluoride nanoparticles with copper alone, successfully preparing copper-doped nickel fluoride (NiF2) nanorods and copper nanoparticles co-modified PCNFs (Cu@NiF2/Cu-PCNFs) as an efficient bi-functional oxygen electrocatalyst. When copper is doped into the PCNFs in the form of metallic nanoparticles, the doped elemental copper can improve the electronic conductivity of composite materials to accelerate electron conduction. Meanwhile, the copper doping for NiF2 can significantly promote the transformation of nickel fluoride nanoparticles into nanorod structures, thus increasing the electrochemical active surface area and enhancing mass diffusion. The Cu-doped NiF2 nanorods also possess an optimized electronic structure, including a more negative d-band center, smaller bandgap width and lower reaction energy barrier. Under the synergistic effect of these advantages, the obtained Cu@NiF2/Cu-PCNFs exhibit outstanding bi-functional catalytic performances, with a low overpotential of 0.68 V and a peak power density of 222 mW cm-2 in zinc-air batteries (ZABs) and stable cycling for 800 h. This work proposes a one-step way based on the dual-doping strategy, providing important guidance for designing and developing efficient catalysts with well-designed architectures for high-performance ZABs.

Fluorine-lodged high-valent high-entropy layered double hydroxide for efficient, long-lasting zinc-air batteries.

Efficient and stable bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts are urgently needed to unlock the full potential of zinc-air batteries (ZABs). High-valence oxides (HVOs) and high entropy oxides (HEOs) are suitable candidates for their optimal electronic structures and stability but suffer from demanding synthesis. Here, a low-cost fluorine-lodged high-valent high-entropy layered double hydroxide (HV-HE-LDH) (FeCoNi2F4(OH)4) is conveniently prepared through multi-ions co-precipitation, where F- are firmly embedded into the individual hydroxide layers. Spectroscopic detections and theoretical simulations reveal high valent metal cations are obtained in FeCoNi2F4(OH)4, which enlarge the energy band overlap between metal 3d and O 2p, enhancing the electronic conductivity and charge transfer, thus affording high intrinsic OER catalytic activity. More importantly, the strengthened metal-oxygen (M-O) bonds and stable octahedral geometry (M-O(F)6) in FeCoNi2F4(OH)4 prevent structural reorganization, rendering long-term catalytic stability. Furthermore, an efficient three-phase reaction interface with fast oxygen transportation was constructed, significantly improving the ORR activity. ZABs assembled with FeCoNi2F4(OH)4@HCC (hydrophobic carbon cloth) cathodes deliver a top performance with high round-trip energy efficiency (60.6% at 10 mA cm-2) and long-term stability (efficiency remains at 58.8% after 1050 charge-discharge cycles).

Large-Scale Atomic Strain Defects on Palladium Surfaces for Enhanced Oxygen Reduction and Zinc-Air Batteries.

Designing nano-electrocatalysts rich in surface defects is critical to improve their catalytic performance. However, prevailing synthesis techniques rely heavily on complex procedures that compromise defect extensiveness and uniformity, casting a high demand for methods capable of synthesizing large-scale crystalline defects. An innovative design strategy is herein proposed that induces ample strain/dislocation defects during the growth of palladium (Pd), which is well-known as a good oxygen reduction reaction (ORR) catalyst. The controlled defect engineering on Pd core is achieved by the tensile stress exerted from an intentionally applied Fe3O4 skin layer during synthesis, which changes the surface free energy of Pd to stabilize the defect presence. With such large-scale crystalline defects, this Pd catalyst exhibits significantly higher ORR activity than commercial Pt/C, enabling its promising future in zinc-air battery catalysis. Additionally, the protective Fe3O4 skin covering the catalyst also enhances its catalytic stability. Theoretical calculations show that the superior catalytic property of such defect-engineered Pd is associated with the correspondingly modified adsorption energy of *O intermediates onto its surface, which further improves the reaction rate and thus boosts ORR kinetics. Findings here are expected to provide a paradigm for designing efficient and stable metal catalysts with plentiful large-scale strain defects.

Manipulating the Electronic Properties of an Fe Single Atom Catalyst via Secondary Coordination Sphere Engineering to Provide Enhanced Oxygen Electrocatalytic Activity in Zinc-Air Batteries.

Oxygen reduction and evolution reactions are two key processes in electrochemical energy conversion technologies. Synthesis of nonprecious metal, carbon-based electrocatalysts with high oxygen bifunctional activity and stability is a crucial, yet challenging step to achieving electrochemical energy conversion. Here, an approach to address this issue: synthesis of an atomically dispersed Fe electrocatalyst (Fe1/NCP) over a porous, defect-containing nitrogen-doped carbon support, is described. Through incorporation of a phosphorus atom into the second coordination sphere of iron, the activity and durability boundaries of this catalyst are pushed to an unprecedented level in alkaline environments, such as those found in a zinc-air battery. The rationale is to delicately incorporate P heteroatoms and defects close to the central metal sites (FeN4P1-OH) in order to break the local symmetry of the electronic distribution. This enables suitable binding strength with oxygenated intermediates. In situ characterizations and theoretical studies demonstrate that these synergetic interactions are responsible for high bifunctional activity and stability. These intrinsic advantages of Fe1/NCP enable a potential gap of a mere 0.65 V and a high power density of 263.8 mW cm-2 when incorporated into a zinc-air battery. These findings underscore the importance of design principles to access high-performance electrocatalysts for green energy technologies.

Ultrafast Conversion of Water and Oxygen Molecules With Dissociation of Hydrogen Bonding Effect to Achieve Extra-High Energy Efficiency of Secondary Metal-Air Batteries.

Metal-air secondary batteries with ultrahigh specific energies have received vast attention and are considered new promising energy storage. The slow redox reactions between oxygen-water molecules lead to low energy efficiency (55-71%) and limited applications. Herein, it is proposed that the MIL-68(In)-derived porous carbon nanotube supports the CoNiFeP heteroconjugated alloy catalyst with an overboiling point electrolyte to achieve the ultrahigh oxidation rate of water molecules. Structural characterization and density functional theory calculations reveal that the new catalyst greatly reduces the free energy of the process, and the overboiling point further accelerates the dissociation of O─H and hydrogen bonds, and the release of O2 molecules, achieving an extra-low overpotential of 110 mV@10 mA cm-2 far lower than commercial Ir/C catalysts of 192 mV at 125 °C and state-of-the-art. Furthermore, the energy efficiency of assembled rechargeable zinc-air batteries begins to break through at 85 °C, jumps at 100 °C, and reaches ultrahigh energy efficiency of 88.1% at 125 °C with an ultralow decay rate of 0.0068% after 150 cycles far superior to those of reported metal-air batteries. This work provides a new catalyst and electrolyte joint-design strategy and reexamines the battery operating temperature to construct higher energy efficiency for secondary fuel cells.

Tailoring Single-Atom Coordination Environments in Carbon Nanofibers via Flash Heating for Highly Efficient Bifunctional Oxygen Electrocatalysis.

The rational design of carbon-supported transition metal single-atom catalysts necessitates precise atomic positioning within the precursor. However, structural collapse during pyrolysis can occlude single atoms, posing significant challenges in controlling both their utilization and coordination environment. Herein, we present a surface atom adsorption-flash heating (FH) strategy, which ensures that the pre-designed carbon nanofiber structure remains intact during heating, preventing unforeseen collapse effects and enabling the formation of metal atoms in nano-environments with either tetra-nitrogen or penta-nitrogen coordination at different flash heating temperatures. Theoretical calculations and in situ Raman spectroscopy reveal that penta-nitrogen coordinated cobalt atoms (Co-N5) promote a lower energy pathway for oxygen reduction and oxygen evolution reactions compared to the commonly formed Co-N4 sites. This strategy ensures that Co-N5 sites are fully exposed on the surface, achieving exceptionally high atomic utilization. The turnover frequency (65.33 s-1) is 47.4 times higher than that of 20% Pt/C under alkaline conditions. The porous, flexible carbon nanofibers significantly enhance zinc-air battery performance, with a high peak power density (273.8 mW cm-2), large specific capacity (784.2 mA h g-1), and long-term cycling stability over 600 h. Additionally, the flexible fiber-shaped zinc-air battery can power wearable devices, demonstrating significant potential in flexible electronics applications.

Promoting Electrocatalytic Oxygen Reactions Using Advanced Heterostructures for Rechargeable Zinc-Air Battery Applications.

In order to facilitate electrochemical oxygen reactions in electrically rechargeable zinc-air batteries (ZABs), there is a need to develop innovative approaches for efficient oxygen electrocatalysts. Due to their reliability, high energy density, material abundance, and ecofriendliness, rechargeable ZABs hold promise as next-generation energy storage and conversion devices. However, the large-scale application of ZABs is currently hindered by the slow kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). However, the development of heterostructure-based electrocatalysts has the potential to surpass the limitations imposed by the intrinsic properties of a single material. This Account begins with an explanation of the configurations of ZABs and the fundamentals of the oxygen electrochemistry of the air electrode. Then, we summarize recent progress with respect to the variety of heterostructures that exploit bifunctional electrocatalytic reactions and overview their impact on ZAB performance. The range of heterointerfacial engineering strategies for improving the ORR/OER and ZAB performance includes tailoring the surface chemistry, dimensionality of catalysts, interfacial charge transfer, mass and charge transport, and morphology. We highlight the multicomponent design approaches that take these features into account to create advanced highly active bifunctional catalysts. Finally, we discuss the challenges and future perspectives on this important topic that aim to enhance the bifunctional activity and performance of zinc-air batteries.

Electrodeposition of Ni/Cu Bimetallic Conductive Metal-Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc-Air Batteries.

Zinc-air batteries employing non-Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal-organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well-aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room-temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn-Teller effect in the doped Cu. The resulting bimetallic Ni2.1Cu0.9(HITP)2 exhibits superior ORR performance, boasting a high onset potential of 0.93 V. Moreover, the assembled aqueous zinc-air battery demonstrates high specific capacity of 706.2 mA h g-1, and exceptional long-term charge/discharge stability exceeding 1250 cycles.

Inclusion Strategy for Constructing S/N Orbital Hybridization-Regulated sp3/sp2 Carbon toward Boost Electrocatalysis.

Metal-free carbon-based electrocatalysts have gained significant attention in the field of zinc-air batteries (ZABs) due to their affordability, good conductivity and chemical stability. However, unmodified carbon materials typically fall short in adsorbing and activating the substrates and intermediates involved in oxygen reduction reactions (ORR). Here, a metal-free carbon-based electrocatalyst with S atom p orbital hybrid modified N-sp3/sp2 carbon structure (C/NS) were prepared by cyclodextrins inclusion. The catalyst demonstrates impressive ORR activity (E1/2=0.885 V vs. RHE) and robust ZABs performance with a power density of 171.3 mW cm-2 and a specific capacity of 781.2 mAh g-1. Density functional theory (DFT) calculation reveals that S atom effectively regulates the charge distribution and p-band center of active site carbon atom in the N-sp3/sp2 carbon structure. This modification prompts the adsorption and dissociation of O2 and intermediates, resulting in higher reactive activity. This work provides a valuable and practical strategy for preparing cost-effective metal-free carbon-based electrocatalysts for ORR with high performance.

CuNi alloy anchored on dual-substrate TiOx/N-doped carbon nanofibers as a bifunctional electrocatalyst for rechargeable zinc-air batteries.

Development of non-noble metal-based electrocatalysts to enhance the performance of zinc-air batteries (ZABs) is of great significance, but it remains a formidable challenge due to their poor stability and activity. Herein, a bifunctional CuNi-TiOx/NCNFS electrocatalyst, featuring with electron-rich copper-nickel (CuNi) alloy nanoparticles anchored on titanium oxide/N-doped carbon nanofibers (TiOx/NCNFS), is constructed by a dual-substrate loading strategy. The introduction of TiOx has led to a significant increase in the stability of the dual-substrate. The strong electronic interaction between CuNi and TiOx strengthens the anchoring of active metal sites, thus accelerating the electron transfer. Theoretical calculations unclose that NCNFS can regulate the charge distribution of TiOx, inducing the charge transfer from NCNFS â†’ TiOx â†’ CuNi, thereby reducing the d-band center of Cu and Ni, which is beneficial to the desorption of intermediate oxide species of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, CuNi-TiOx/NCNFS delivers a remarkable bifunctional performance with a low OER overpotential of 258 mV at 10 mA cm-2 and an ORR half-wave potential of 0.85  V. When assembled into ZABs, CuNi-TiOx/NCNFS shows a low potential gap of 0.64 V, a higher power density of 149.6 mW cm-2 at 330 mA cm-2, and an outstanding stability for 250 h at 5mA cm-2. This study provides a novel approach by constructing dual-substrate to tune the electronic structure of active metal sites for efficient rechargeable ZABs.

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) = 0.878 V and limiting current density (JL) = 21.88 mA cm-2). The JL exceeds the 20 wt% Pt/C (19.34 mA cm-2) and the E1/2 is close to the 20 wt% Pt/C (0.881 V). It also possesses excellent oxygen evolution reaction (OER) performance (overpotential of 324 mV@10 mA cm-2), which even exceeds that of the commercial RuO2 (427 mV@10 mA cm-2). The density functional theory calculation 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 138.29 mW cm-2, outperforming the 20 wt% Pt/C+RuO2 (73.9 mW cm-2) and other recently reported catalysts. Furthermore, all-solid-state ZAB delivers a high peak power density of 64.83 mW cm-2 and ultra-robust cycling stability even under bending.

N-regulated three-dimensional turf-like carbon nanosheet loaded with FeCoNi nanoalloys as bifunctional electrocatalysts for durable zinc-air batteries.

N-regulated three-dimensional (3D) turf-like carbon material loaded with FeCoNi nanoalloys (F-CNS-CNT), composed of carbon nanotubes (CNT) grown in situ on carbon nanosheets(CNS), was synthesized using a low-temperature solution combustion method and organic compounds rich in pyridinic-N. This distinct structure significantly expands the effective electrochemical surface area, revealing an abundance of active sites and enhancing the mass transfer capability for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Both experimental observations and theoretical calculations corroborate that the synergy between the FeCoNi nanoalloy and the highly pyridinic N-doped carbon substrate optimizes the adsorption and desorption-free energy of oxygen intermediates, resulting in a remarkable improvement of intrinsic ORR/OER activity. Therefore, the derived F-CNS-CNT electrocatalyst can present a favorable half-wave potential of 0.85 V (ORR) and a lower overpotential of 260 mV (corresponding to a current density of 10 mA cm-2, OER) in alkaline media. Moreover, when employed in the air cathode of a flowable zinc-air battery, the electrocatalyst exhibits exceptional discharge and charge performance, including a high power density of 144.6 mW cm-2, a high specific capacity of 801 mAh g-1, and an impressive cycling stability of 600 cycles at a current density of 10 mA cm-2. Notably, these results markedly surpass those of the commercial catalyst Pt/C + IrO2.

Electron Spin Broken-Symmetry of Fe-Co Diatomic Pairs to Promote Kinetics of Bifunctional Oxygen Electrocatalysis for Zinc-Air Batteries.

Designing bifunctional catalysts to reduce the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) reaction barriers while accelerating the reaction kinetics is perceived to be a promising strategy to improve the performance of Zinc-air batteries. Unsymmetric configuration in single-atom catalysts has attracted attention due to its unique advantages in regulating electron orbitals. In this work, a seesaw effect in unsymmetric Fe-Co bimetallic monoatomic configurations is proposed, which can effectively improve the OER/ORR bifunctional activity of the catalyst. Compared with the symmetrical model of Fe-Co, a strong charge polarization between Co and Fe atoms in the unsymmetric model is detected, in whom the spin-down electrons around Co atoms are much higher than those spin-up electrons. The seesaw effect occurred between Co atoms and Fe atoms, resulting in a negative shift of the d-band center, which means that the adsorption of oxygen intermediates is weakened and more conducive to their dissociation. The optimized reaction kinetics of the catalyst leads to excellent performance in ZABs, with a peak power density of 215 mW cm-2 and stable cycling for >1300 h and >4000 cycles. Flexible Zinc-air batteries have also gained excellent performance to demonstrate their potential in the field of flexible wearables.

Graphdiyne-Induced CoN/CoS2 Heterojunction: Boosting Efficiency for Bifunctional Oxygen Electrochemistry in Zinc-Air Batteries.

The performance of zinc-air battery is constrained by the sluggish rate of oxygen electrode reaction, particularly under high current discharge conditions where the kinetic process of the oxygen reduction reaction (ORR) decelerates significantly. To address this challenge, we present a novel phase transition strategy that facilitates the creation of a heteroatom-doped heterointerface (CoN/CoS2). The meticulously engineered CoN/CoS2/NC electrocatalyst displays a superior ORR half-wave potential of 0.87 V and an OER overpotential of 320 mV at 10 mA cm-2. Experimental and computational analysis confirm that the CoN/CoS2 heterostructure optimizes local charge distribution, accelerates electron transfer, and tunes active sites for enhanced catalysis. Notably, this heterojunction improves stability by resisting corrosion and degradation under harsh alkaline conditions, thus demonstrating superior performance and longevity in a custom-made liquid zinc-air battery. This research provides valuable practical and theoretical foundations for designing efficient heterointerfaces in electrocatalysis applications.

Asymmetric Coordination of Bimetallic Fe-Co Single-Atom Pairs toward Enhanced Bifunctional Activity for Rechargeable Zinc-Air Batteries.

The advancement of rechargeable zinc-air batteries (RZABs) faces challenges from the pronounced polarization and sluggish kinetics of oxygen reduction and evolution reactions (ORR and OER). Single-atom catalysts offer an effective solution, yet their insufficient or singular catalytic activity hinders their development. In this work, a dual single-atom catalyst, FeCo-SAs, was fabricated, featuring atomically dispersed N3-Fe-Co-N4 sites on N-doped graphene nanosheets for bifunctional activity. Introducing Co into Fe single-atoms and secondary pyrolysis altered Fe coordination with N, creating an asymmetric environment that promoted charge transfer and increased the density of states near the Fermi level. This catalyst achieved a narrow potential gap of 0.616 V, with a half-wave potential of 0.884 V for ORR (vs the reversible hydrogen electrode) and a low OER overpotential of 270 mV at 10 mA cm-2. Owing to the superior activity of FeCo-SAs, RZABs exhibited a peak power density of 203.36 mW cm-2 and an extended cycle life of over 550 h, exceeding the commercial Pt/C + IrO2 catalyst. Furthermore, flexible RZABs with FeCo-SAs demonstrated the promising future of bimetallic pairs in wearable energy storage devices.