Bifunctional Covalent Organic Framework-Derived Electrocatalysts with Modulated p-Band Centers for Rechargeable Zn–Air Batteries

Fine control over the physicochemical structures of carbon electrocatalysts is important for improving the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn–air batteries. Covalent organic frameworks (COFs) are considered good candidate carbon materials because their structures can be precisely controlled. However, it remains a challenge to impart bifunctional electrocatalytic activities for both the ORR and OER to COFs. Herein, a pyridine-linked triazine covalent organic framework (PTCOF) with well-defined active sites and pores is readily prepared under mild conditions, and its electronic structure is modulated by incorporating Co nanoparticles (CoNP-PTCOF) to induce bifunctional electrocatalytic activities for the ORR and OER. The CoNP-PTCOF exhibits lower overpotentials for both ORR and OER with outstanding stability. Computational simulations find that the p-band center of CoNP-PTCOF down-shifted by charge transfer, compared to pristine PTCOF, facilitate the adsorption and desorption of oxygen intermediates on the pyridinic carbon active sites during the reactions. The Zn–air battery assembled with bifunctional CoNP-PTCOF exhibits a small voltage gap of 0.83 V and superior durability for 720 cycles as compared with a battery containing commercial Pt/C and RuO₂. This strategy for modulating COF electrocatalytic activities can be extended for designing diverse carbon electrocatalysts.     

MO‐Co@N‐Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn–Air Battery

A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal–air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO‐Co@N‐doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal–organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co–N_x and Co³⁺/Co²⁺ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn‐based and Co‐based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (≥700 °C), which is favorable for charge transfer. The optimized CoZn‐NC‐700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO₂ (for OER). CoZn‐NC‐700 also exhibits the prominent Zn–air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO₂.     

Inhibiting Surface Diffusion to Synthesize 3D Bicontinuous Nanoporous N-Doped Carbon for Boosting Oxygen Reduction Reaction in Flexible All-Solid-State Al-Air Batteries

Catalyzing oxygen reduction reaction (ORR) and accelerating oxygen diffusion are two key challenges for the requirements of the cathode catalysts in the metal-air batteries. A promising strategy for improving both ORR performance and mass diffusion simultaneously is to build carbon-based catalysts with ORR-active chemical dopants and 3D interconnected porosity. Herein, a 3D nanoporous N-doped carbon with bicontinuous porosity and interconnected open-pore channels is reported, which is prepared by a polyaniline-assisted template method. The polyaniline can efficiently inhibit the surface diffusion-caused template coarsening, achieving a small pore size of 35 nm. The small porous morphology gives rise to a high N-dopant concentration up to 7.20 at.%, which in turn exhibits a commercial Pt/C-comparable ORR performance together with satisfied durability in alkaline media. Using these nanoporous carbon catalysts as air electrodes, an all-solid-state flexible Al-air battery is assembled with the measured maximum power density reaching 130.5 mW cm⁻², as compared to 106.2 mW cm⁻² when the commercial Pt/C standard is used. This study provides an efficient method to synthesize 3D N-doped carbon with bicontinuous nano-sized pore channels for wide-ranging applications in portable and flexible devices.     

Revisiting the Role of Sulfur Functionality in Regulating the Electron Distribution of Single-Atomic Fe Sites Toward Enhanced Oxygen Reduction

Introducing sulfur functionalities is reported as an efficacious route to regulate the electron distribution of single-atomic Fe sites for improving the oxygen reduction reaction (ORR) activity, however, it remains controversial about the role of type of sulfur functionalities in enhancing the ORR activity. Herein, this study revisits the role of sulfur functionalities in regulating the electron distribution of single-atomic Fe sites by the construction of single-atomic Fe-N₄ sites with sulfur functionalities (FeSNC) using sulfur-containing molecules with different molecular structures. X-ray absorption spectroscopy and theoretical calculations confirm that thiophene S and oxidized S both possess the electron-donating properties for regulating the electronic distribution of Fe-N₄ sites, which is beneficial to weaken the adsorption of the ORR intermediates. As expected, the optimal FeSNC has attractive ORR activity with half-potential of 0.76 V in 0.5 m H₂SO₄ and 0.91 V in 0.1 m KOH along with remarkable Zn-air battery performance. Moreover, the developed synthetic method has also been extended to construct B and P regulated FeNC catalysts.     

Polyformamidine‐Derived Non‐Noble Metal Electrocatalysts for Efficient Oxygen Reduction Reaction

A facile approach for the template‐free synthesis of highly active non‐noble metal based oxygen reduction reaction (ORR) electrocatalysts is presented. Porous Fe?N?C/Fe/Fe₃C composite materials are obtained by pyrolysis of defined precursor mixtures of polyformamidine (PFA) and FeCl₃ as nitrogen‐rich carbon and iron sources, respectively. Selection of pyrolysis temperature (700–1100 °C) and FeCl₃ loading (5–30 wt%) yields materials with differing surface areas, porosity, graphitization degree, nitrogen and iron content, as well as ORR activity. While the ORR activity of Fe‐free materials is limited (i.e., synthesized from pure PFA), a huge increase in activity is observed for catalysts containing Fe, revealing the participation of the metal dopant in the construction of active electrocatalytic sites. Further activity improvement is achieved via acid‐leaching and repeated pyrolysis, a result which is attributed to the creation of new active sites located at the surface of the porous nitrogen‐doped carbon by dissolution of the Fe and Fe₃C nanophases. The best performing catalyst, which was synthesized with a low Fe loading (i.e., 5 wt%) and at a pyrolysis temperature of 900 °C, exhibits high activity, excellent H₂O selectivity, extended stability, in both basic and acidic media as well as a remarkable tolerance toward methanol.     

Understanding the Synergistic Effects of Cobalt Single Atoms and Small Nanoparticles: Enhancing Oxygen Reduction Reaction Catalytic Activity and Stability for Zinc-Air Batteries

The development of earth-abundant oxygen reduction reaction (ORR) catalysts with high catalytic activity and good stability for practical metal-air batteries remains an enormous challenge. Herein, a highly efficient and durable ORR catalyst is reported, which consists of atomically dispersed Co single atoms (Co-SAs) in the form of Co-N4 moieties and small Co nanoparticles (Co-SNPs) co-anchored on nitrogen-doped porous carbon nanocage (Co-SAs/SNPs@NC). Benefiting from the synergistic effect of Co-SAs and Co-SNPs as well as the enhanced anticorrosion capability of the carbon matrix brought by its improved graphitization degree, the resultant Co-SAs/SNPs@NC catalyst exhibits outstanding ORR activity and remarkable stability in alkaline media, outperforming Co-SAs-based catalyst (Co-SAs@NC), and benchmark Pt/C catalyst. Density functional theory calculations reveal that the strong interaction between Co-SNPs and Co-N4 sites can increase the valence state of the active Co atoms in Co-SAs/SNPs@NC and moderate the adsorption free energy of ORR intermediates, thus facilitating the reduction of O₂. Moreover, the practical zinc-air battery assembled with Co-SAs/SNPs@NC catalyst demonstrates a maximum power density of 223.5 mW cm^–2, a high specific capacity of 742 W h kg^–1 at 50 mA cm^–2 and a superior cycling stability.     

Blood Ties: Co3O4 Decorated Blood Derived Carbon as a Superior Bifunctional Electrocatalyst

A simple, versatile and cheap synthetic route is demonstrated for the preparation of Co₃O₄ decorated blood powder derived heteroatom doped porous carbon (BDHC). The inorganic hybrid performs well as an advanced bifunctional non‐precious metal electrocatalyst. The hybridization of Co₃O₄ with the blood‐derived carbon results in improved activities not only towards the oxygen reduction reaction (ORR), but also in the reverse oxygen evolution reaction (OER). An improved ORR activity and a tuned four electron transfer selectivity can be assigned to a synergistic catalytic effect due the intimate contact between Co₃O­₄ particles and the highly conductive heteroatom doped carbon support, mediated by cobalt‐nitrogen or cobalt‐phosphorous coordination sites. This heterojunction may facilitate the electron transfer by preventing an accumulation of electron density within the Co₃O­₄ particles. The straight‐forward and cheap synthesis of the highly active and durable electrocatalyst make it a promising candidate for a next‐generation bifunctional electrocatalyst for applications such as reversible fuel cells/electrolyzers or metal air batteries.     

Dual-Sites Coordination Engineering of Single Atom Catalysts for Full-Temperature Adaptive Flexible Ultralong-Life Solid-State Zn−Air Batteries

High-performance rechargeable Zn-air batteries with long-life stability are desirable for power applications in electric vehicles. The key component of the Zn-air batteries is the bifunctional oxygen electrocatalyst, however, designing a bifunctional oxygen electrocatalyst with high intrinsic reversibility and durability is a challenge. Through density functional theory calculations, it is found that the catalytic activity originated from the electronic and geometric coordination structures synergistic effect of the Fe and Co dual-sites with metal-N₄ coordination environment, assisting the stronger hybridization of electronic orbitals between Co (dxz, dz²) and OO* (px, pz), thus making the stronger O₂ active ability of Co active site. These findings enable to development of a fancy dual single-atom catalyst comprising adjacent Fe N₄ and Co N₄ sites on N-doped carbon matrix (FeCo-NC). FeCo-NC exhibits extraordinary bifunctional activities for oxygen reduction and evolution reaction (ORR/OER), which displays high half-wave potential (0.893 V) for the ORR, and low overpotential (343 mV) at 10 mA cm⁻² for the OER. The assembled FeCo-NC air-electrode works well in the flexible solid-state Zn-air battery with a high specific capacity of 747.0 mAh g⁻¹, a long-time stability of more than 400 h (30 °C), and also a superior performance at extreme temperatures (−30 °C–60 °C).     

Neutral Zn-Air Battery Assembled with Single-Atom Iridium Catalysts for Sensitive Self-Powered Sensing System

Self-powered sensing systems (SPSSs) are critical components in smart portable electronic devices. Zinc-air batteries (ZABs) as promising energy devices provide a great opportunity to develop novel SPSS for sensing applications owing to the merit of high open-circuit potential. Herein, hierarchically porous single-atom iridium embedded nitrogen-doped carbon (SA-Ir/NC) is reported as an efficient catalyst for the oxygen reduction reaction (ORR) in the neutral ZABs, enabling the SPSSs towards glucose detection with a high sensitivity and stable output signal. The resultant SA-Ir/NC shows superior ORR activity and stability to commercial Pt/C in neutral electrolytes. According to the theoretical calculations, IrN₅ active sites in SA-Ir/NC exhibit moderate adsorption free energy to reaction intermediates, giving SA-Ir/NC excellent four-electron ORR activity and well-enhanced H₂O₂ tolerance. When SA-Ir/NC is applied as an air cathode, the as-prepared ZABs display a large open-circuit voltage of 1.42 V, a remarkable power density of 90.4 mW cm⁻², and excellent long-term stability. After being integrated with glucose oxidase, the SPSSs are successfully established for sensitive detection of glucose based on a competitive model, holding great promise in biosensing applications.     

Steering Local Electronic Configuration of Fe–N–C-Based Coupling Catalysts via Ligand Engineering for Efficient Oxygen Electroreduction

Fe–N–C materials are prospective candidates to displace platinum-group-based oxygen reduction reaction (ORR) catalysts, but their application is still impeded by the conundrums of unsatisfactory activity and stability. Herein, a feasible strategy of ligand engineering of the metal-organic framework is proposed to steer the local electronic configuration of Fe–N–C-based coupling catalysts by incorporating engineered sulfur functionalities. The obtained catalysts with rich Fe-N₄ sites and FeS nanoparticles are embedded on N/S-doped carbon (denoted as FeS/FeNSC). In this unique structure, the engineered FeS nanoparticles and oxidized sulfur synergistically induce electron redistribution and modulate electronic configuration of Fe-N₄ sites, contributing to substantially accelerated kinetics and improved activity. Consequently, the optimized FeS/FeNSC catalyst displays outstanding ORR performance with a half-wave potential of 0.91 V, better four electron pathway selectivity, lower H₂O₂ yield, and superior long-term stability. As a proof-of-concept, zinc-air batteries based on FeS/FeNSC deliver high capacity of 807.54 mA h g⁻¹, a remarkable peak power density of 256.06 mW cm⁻², and outstanding cycling stability over 600 h at 20 mA cm⁻². This study delivers an efficacious approach to manipulate the electronic configuration of Fe–N–C catalysts toward elevated catalytic activity and stability for various energy conversion/storage devices.     

Local Geometric Distortion to Stimulate Oxygen Reduction Activity of Atomically Dispersed Zn-Nx Sites for Zn–Air Batteries

Local geometric strain engineering is useful for modulating the performance of nitrogen-coordinated transition metal-carbon catalysts. However, realizing the nano-level strain is technically challenging. Additionally, the structure-property relationship between strain degree and performance remains poorly understood. Herein, it is conceptually predict that geometric bending induces more electron transfer from Zn to the coordinated N in Zn─N─C, leading to a positive shift of the d-band center of the Zn atom, which promotes the adsorption reduction process of the O₂ molecule and thus increases the intrinsic oxygen reduction reaction (ORR) activity. Moreover, a low-temperature non-saturated coordination strategy is proposed to prepare spherical porous carbon catalysts with surface-enriched geometrically bent (20-50°) Zn─N─C sites. Benefiting from the highly active Zn─N─C sites, large specific surface area and abundant pore structure, the optimized catalyst (S─Zn─N─C-950) exhibited excellent intrinsic alkaline ORR activity (half-wave potential E_1/2 = 0.89 V) and high zinc-air battery performance (peak power density of 229.2 mW cm⁻²), exceeding that of commercial Pt/C catalysts. Density functional theory (DFT) calculations show that when the geometrical bending angle is 30–45°, Zn centers with suitable charge transfer to the surrounding N can produce a moderate adsorption strength to the oxygen intermediate state, resulting in optimal ORR activity.     

Fe,Cu‐Coordinated ZIF‐Derived Carbon Framework for Efficient Oxygen Reduction Reaction and Zinc–Air Batteries

Zeolitic imidazole frameworks (ZIFs) offer rich platforms for rational design and construction of high‐performance nonprecious‐metal oxygen reduction reaction (ORR) catalysts owing to their flexibility, hierarchical porous structures, and high surface area. Herein, an Fe, Cu‐coordinated ZIF‐derived carbon framework (Cu@Fe‐N‐C) with a well‐defined morphology of truncated rhombic dodecahedron is facilely prepared by introducing Fe²⁺ and Cu²⁺ during the growth of ZIF‐8, followed by pyrolysis. The obtained Cu@Fe‐N‐C, with bimetallic active sites, large surface area, high nitrogen doping level, and conductive carbon frameworks, exhibits excellent ORR performance. It displays 50 mV higher half‐wave potential (0.892 V) than that of Pt catalysts in an alkaline medium and comparable performance to Pt catalysts in an acidic medium. In addition, it also has excellent durability and methanol resistance ability in both acidic and alkaline solutions, which makes it one of the best Pt‐free catalysts reported to date for ORR. Impressively, when being employed as a cathode catalyst in zinc–air batteries, Cu@Fe‐N‐C presents a higher peak power density of 92 mW cm^?2 than that of Pt/C (74 mW cm^?2) as well as excellent durability.     

High-Loading Co Single Atoms and Clusters Active Sites toward Enhanced Electrocatalysis of Oxygen Reduction Reaction for High-Performance Zn–Air Battery

The development of precious-metal alternative electrocatalysts for oxygen reduction reaction (ORR) is highly desired for a variety of fuel cells, and single atom catalysts (SACs) have been envisaged to be the promising choice. However, there remains challenges in the synthesis of high metal loading SACs (>5 wt.%), thus limiting their electrocatalytic performance. Herein, a facile self-sacrificing template strategy is developed for fabricating Co single atoms along with Co atomic clusters co-anchored on porous-rich nitrogen-doped graphene (Co SAs/AC@NG), which is implemented by the pyrolysis of dicyandiamide with the formation of layered g-C₃N₄ as sacrificed templates, providing rich anchoring sites to achieve high Co loading up to 14.0 wt.% in Co SAs/AC@NG. Experiments combined with density functional theory calculations reveal that the co-existence of Co single atoms and clusters with underlying nitrogen doped carbon in the optimized Co₄₀SAs/AC@NG synergistically contributes to the enhanced electrocatalysis for ORR, which outperforms the state-of-the-art Pt/C catalysts with presenting a high half-wave potential (E_1/2 = 0.890 V) and robust long-term stability. Moreover, the Co₄₀SAs/AC@NG presents excellent performance in Zn–air battery with a high-peak power density (221 mW cm⁻²) and strong cycling stability, demonstrating great potential for energy storage applications.     

Single‐Atom Catalysts for Electrocatalytic Applications

The recent advances in electrocatalysis for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), carbon dioxide reduction reaction (CO₂RR), and nitrogen reduction reaction (NRR) are thoroughly reviewed. This comprehensive review focuses on the single‐atom catalysts (SACs) including Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, W, Bi, Ru, Rh, Pd, Ag, Ir, Pt, and Au with single‐metal sites or dual‐metal sites. The recent development of single‐atom electrocatalysts with novel configurations and compositions is documented. The understanding of the process–structure–property relationships is highlighted. For the SACs, their electrocatalytic performance and stability in fuel cells, zinc–air batteries, electrolyzers, CO₂RR, and NRR are summarized. The challenges and perspectives in the emerging field of single‐atom electrocatalysis are discussed.     

Metal (Ni,Co)‐Metal Oxides/Graphene Nanocomposites as Multifunctional Electrocatalysts

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) along with hydrogen evolution reaction (HER) have been considered critical processes for electrochemical energy conversion and storage through metal‐air battery, fuel cell, and water electrolyzer technologies. Here, a new class of multifunctional electrocatalysts consisting of dominant metallic Ni or Co with small fraction of their oxides anchored onto nitrogen‐doped reduced graphene oxide (rGO) including Co‐CoO/N‐rGO and Ni‐NiO/N‐rGO are prepared via a pyrolysis of graphene oxide and cobalt or nickel salts. Ni‐NiO/N‐rGO shows the higher electrocatalytic activity for the OER in 0.1 m KOH with a low overpotential of 0.24 V at a current density of 10 mA cm^?2, which is superior to that of the commercial IrO₂. In addition, it exhibits remarkable activity for the HER, demonstrating a low overpotential of 0.16 V at a current density of 20 mA cm^?2 in 1.0 m KOH. Apart from similar HER activity to the Ni‐based catalyst, Co‐CoO/N‐rGO displays the higher activity for the ORR, comparable to Pt/C in zinc‐air batteries. This work provides a new avenue for the development of multifunctional electrocatalysts with optimal catalytic activity by varying transition metals (Ni or Co) for these highly demanded electrochemical energy technologies.     

Porous Carbons: Structure‐Oriented Design and Versatile Applications

Porous carbon materials have demonstrated exceptional performance in a variety of energy‐ and environment‐related applications. Over the past decades, tremendous efforts have been made in the coordinated design and fabrication of porous carbon nanoarchitectures in terms of pore sizes, surface chemistry, and structure. Herein, structure‐oriented carbon design and applications are reviewed. The unique properties of porous carbon materials that offer them promising design opportunities and broad applicability in some representative fields, including water remediation, CO₂ capture, lithium‐ion batteries, lithium–sulfur batteries, lithium metal anodes, Na‐ion batteries, K‐ion batteries, supercapacitors, and the oxygen reduction reaction are highlighted. Then, the most up‐to‐date strategies for structural control and functionalization of porous carbons are summarized, toward tailoring microporous, mesoporous, macroporous, and hierarchically porous carbons with disordered or ordered, amorphous or graphitic structures. Meanwhile, the emerging features of these structures in various applications are introduced where applicable. Finally, insights into the challenges and perspectives for future development are provided.     

Sub-2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Developing an efficient bifunctional electrocatalyst with accelerated kinetics is important but challenging for rechargeable metal-air batteries. In this study, a series of anion-regulated sub-2 nm ultrathin thiophosphate nanosheets (NiPS_3–xSe_x NSs) is rationally designed and synthesized as bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts for Zn-air batteries. The increase of nominal Se dopants (0 ≤ x ≤ 0.5) leads to the expansion of (001) crystal plane spacing and partially disordered structure generation after the incorporation of Se to pristine NiPS₃. More importantly, electronic structures of active sites can be reasonably regulated via coordination of the interaction between anions and cations. Density functional theory calculations reveal that such tailored electronic structures reduce the overpotential of the thermodynamic barriers step for both OER and ORR as well as shorten energy bandgap, which can accelerate reaction kinetics in electrocatalytic processes and enhance electrical conductivity. Consequently, the obtained NiPS_3–xSe_x NSs exhibit low OER overpotential (250 mV) and positive ORR onset potential (0.94 V), large power density (152 mW cm⁻²), and robust stability (96 h cycle) for Zn-air devices, far exceeding that of precious metal catalysts. This study provides a novel tactic to design earth-abundant and highly efficient bifunctional electrocatalysts for metal-air battery technologies.     

A Universal Strategy Toward Low-Cost Aqueous Sulfur–Iodine Batteries

Rechargeable aqueous batteries with non-toxic and non-flammable features are promising candidates for large-scale energy storage. However, their practical applications are impeded by the insufficient electrochemical stability windows of aqueous electrolytes and intrinsic drawbacks of current electrodes. Herein, an aqueous sulfur–iodine chemistry that can be deployed in aqueous battery systems by employing water-in-bisalt (WiBS) electrolyte, sulfur composite anode, and iodine composite cathode is demonstrated. The freestanding iodine/carbon cloth cathode and halide-containing WiBS electrolyte can support the continuous I⁺/I⁰ reaction by forming interhalogen. Meanwhile, the highly-concentrated electrolyte and inorganic-based solid electrolyte interphase can effectively suppress the dissolution/diffusion of polysulfides, thus realizing S/S_x²⁻ conversion reactions on the anode. Therefore, the as-assembled aqueous sulfur–iodine batteries based on S/S_x²⁻ and I⁺/I⁰ redox couples can deliver a high energy density of 158.7 Wh kg⁻¹ with a considerable cycling performance and safety. Furthermore, this chemistry can be further extended to multivalent ion-based battery systems. As demonstration models, Ca-based and Al-based aqueous sulfur–iodine batteries are also fabricated, which provide a new avenue towards the development of aqueous batteries for low-cost and highly safe energy storage.     

Anchoring Single Copper Atoms to Microporous Carbon Spheres as High-Performance Electrocatalyst for Oxygen Reduction Reaction

Although the carbon-supported single-atom (SA) electrocatalysts (SAECs) have emerged as a new form of highly efficient oxygen reduction reaction (ORR) electrocatalysts, the preferable sites of carbon support for anchoring SAs are somewhat elusive. Here, a KOH activation approach is reported to create abundant defects/vacancies on the porous graphitic carbon nanosphere (CNS) with selective adsorption capability toward transition-metal (TM) ions and innovatively utilize the created defects/vacancies to controllably anchor TM–SAs on the activated CNS via TM N_x coordination bonds. The synthesized TM-based SAECs (TM-SAs@N-CNS, TM: Cu, Fe, Co, and Ni) possess superior ORR electrocatalytic activities. The Cu-SAs@N-CNS demonstrates excellent ORR and oxygen evolution reaction (OER) bifunctional electrocatalytic activities and is successfully applied as a highly efficient air cathode material for the Zn–air battery. Importantly, it is proposed and validated that the N-terminated vacancies on graphitic carbons are the preferable sites to anchor Cu-SAs via a Cu (N C₂)₃(N C) coordination configuration with an excellent promotional effect toward ORR. This synthetic approach exemplifies the expediency of suitable defects/vacancies creation for the fabrication of high-performance TM-based SAECs, which can be implemented for the synthesis of other carbon-supported SAECs.     

Boosting Redox Kinetics of Sulfur Electrochemistry by Manipulating Interfacial Charge Redistribution and Multiple Spatial Confinement in Mott–Schottky Electrocatalysts

The serious shuttle effect and sluggish reaction kinetics intrinsically handicap the practical application of Li-S batteries. Herein, a unique 3D hierarchically porous Mott–Schottky electrocatalyst composed of W₂C quantum dots (QD) spatially confined in nitrogen-doped graphene microspheres (NGM) is proposed for regulating the kinetics of sulfur electrochemistry. Experimental and theoretical results disclose a spontaneous charge rearrangement and induce built-in electric field across the W₂C QD/NGM heterojunction interface, contributing to reduced energy barrier for both polysulfides reduction and Li₂S oxidation during entitle discharge/charge processes. Furthermore, the ultrasmall W₂C QD with high electrocatalytic activity and superior conductivity can promote the conversion of S species, while the hierarchically porous microspheres assembled from wrinkled graphene nanosheets not only can efficiently inhibit the polysulfides shuttling via multiple spatial confinement, but also provide abundant inner space for stable reservation of active S, highly conductive networks, and maintain the structural integrity of cathode during consecutive cycling. Consequently, Li-S batteries employed with the designed W₂C QD/NGM-based cathode exhibit outstanding electrochemical properties even at a high sulfur loading. The superior performance combined with the simplicity of the synthesis process represents a promising strategy for the rational design of advanced electrocatalyst for energy applications.