Efficient Oxygen Reduction Reaction Research Articles

High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 with tailored eg occupancy and transition metal-oxygen bond properties for oxygen reduction reaction

Forming high entropy oxide provides a feasible approach to finding a balance among moderate eg occupancy, high transition metal-oxygen (TM-O) covalency, and lattice energy, which is essential to ensure efficient and durable oxygen reduction reaction (ORR) process for perovskite lanthanide-transition metal oxides (LaTMO3). However, due to the compositional complexity, clarifying the relevance among the high entropy components, eg occupancy, TM-O properties, and ORR performance still remains a challenge. Herein, adopting the B site entropy-driven strategy, a series of LaTMO3 (TM = Cr, Mn, Fe, Co, Ni) with tunable eg occupancy and TM-O bond properties are synthesized, and the correlations between high entropy elements, eg occupancy, TM-O properties, and ORR performances are revealed quantitively based on the crystal field theory and the Phillips–Van Vechten–Levine (P–V–L) valence bond theory. High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 delivers a low overpotential of 493 mV (vs. 503 mV for LaMnO3) and a minuscule decline by only 1.7% (vs. 4.4% for LaMnO3) in half wave potential after 10,000 cycles, which can be associated with the tailored eg occupancy (1.06) and the significant enhancement in both TM-O covalency (4%) and lattice energy (691.75 kJ mol–1). This work not only demonstrates the prospects of high entropy LaTMO3 in the ORR field but also provides a new perspective for the quantitative analysis of the structure-activity relationship for high entropy oxide ORR catalysts.

Strain effect induced Pd nanoparticles decorated Pd2+-doped Co3O4 nanosheets for efficient electrocatalytic ethanol oxidation and oxygen reduction reactions

Reactive metal-support interaction (RMSI) is an effective means of inducing surface strain and charge transfer in catalysts, which further enhances electrochemical activity and modulates reaction pathways. Nevertheless, the precise synthesis of nanomaterials with tunable strain and unique morphology remains a challenge. In this work, we have synthesized Pd nanoparticles decorated Pd2+- doped Co3O4 nanosheets (Pd7.4%/Co3O4) by a NaBH4 reduction method, which exhibit excellent performance for ethanol oxidation reaction (EOR) and oxygen reduction reaction (ORR). The introduction of the Pd into the Co3O4 by the means of elemental doping and nanoparticle decoration, and the resulting lattice strain and electron redistribution are responsible for the improved performance. Meanwhile, Pd7.4%/Co3O4 has a relatively low d-band center that reduces the adsorption energy of reaction intermediates to improve reaction selectivity and eliminate EOR toxic intermediates, ultimately promoting reaction kinetics. This work demonstrates a simple and effective strategy to manipulate lattice strain and electronic coupling and provides a novel and advanced way for the development of low-cost and high-quality direct ethanol fuel cells (DEFCs) catalysts.

Regulating d-Orbital Hybridization of Subgroup-IVB Single Atoms for Efficient Oxygen Reduction Reaction.

Highly active single-atom electrocatalysts for the oxygen reduction reaction are crucial for improving the energy conversion efficiency, but they suffer from a limited choice of metal centers and unsatisfactory stabilities. Here, this work reports that optimization of the binding energies for reaction intermediates by tuning the d-orbital hybridization with axial groups converts inactive subgroup-IVB (Ti, Zr, Hf) moieties (MN4) into active motifs (MN4O), as confirmed with theoretical calculations. The competition between metal-ligand covalency and metal-intermediate covalency affects the d-p orbital hybridization between the metal site and the intermediates, converting the metal centers into active sites. Subsequently, dispersed single-atom M sites coordinated by nitrogen/oxygen groups have been prepared on graphene (s-M-N/O-C) catalysts on a large-scale with high-energy milling and pyrolysis. Impressively, the s-Hf-N/O-C catalyst with 5.08wt% Hf exhibits a half-wave potential of 0.920V and encouraging performance in a zinc-air battery with an extraordinary cycling life of over 1600h and a large peak power-density of 256.9mW cm-2. This work provides promising single-atom electrocatalysts and principles for preparing other catalysts for the oxygen reduction reaction.

Short nanotubular Fe-N-C catalysts with curved catalytic sites and contributing regions for oxygen reduction reaction

The substantial advances of non-precious Fe-N-C materials with both high activity and stability to replace platinum-based catalysts for oxygen reduction reaction (ORR) in fuel cells remain a great challenge, since their intrinsic active site design and contributing microstructure exploration are still unclear. Herein, we propose a solid-phase thermal migration strategy to synthesize Fe, N co-doped nanocarbons with a short nanotubular structure, using ferrocene as Fe source and polyaniline (PANI) as N-doped carbon nanotubes (NCNTs) source. In acidic and alkaline environments, the thermally activated Fe-N-C exhibits efficient ORR performance, and half-wave potential is 30 mV higher than a commercial Pt/C (JM, 20 wt% Pt) in alkaline medium and only 100 mV less than the Pt/C in acidic media. Impressively, the catalyst used in zinc-air battery exhibits an outstanding power density of 144.74 mW·cm−2, higher than the one assembled by the Pt/C (125.67 mW·cm−2). Combining experimental and density functional theory (DFT) calculation results, the superior ORR activity should be attributed to the formation of the efficient off-plane Fe-pyridinic-N4 species at end of the nanotubes. More important, these zigzag-type Fe-pyridinic-N4 sites at the end regions serve as the main active sites, leading to a higher ORR activity. This work opens a door to clarify the active catalytic site types and the contributing microregions of the Fe-N-C catalysts, providing ideas for designing non-noble metal catalysts with curved surfaces and rich edge structures.

Synergy of porous network nanostructuring and nonmetallic phosphorus alloying for efficient oxygen reduction of platinum

Alloying of nanostructured platinum (Pt)-based electrocatalysts can significantly improve their electrocatalytic performance for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, there are few studies of nonmetals alloyed Pt-based nanostructures for ORR electrocatalysis. Herein, we present a synergy of porous network nanostructuring and nonmetallic phosphorus (P) alloying to engineer the high-performance P-alloyed Pt nanospheres (P-PtNSs) for efficient ORR electrocatalysis. This characteristic porous network nanostructure is crafted through surfactant soft-templates induced confinement growth, and P-alloying is realized by a post-phosphating method. The introduction of P into Pt lattice can not only regulate electronic and geometric structure but also augment electrocatalytic active sites through the contribution of Pt-P bonds. The resultant P-PtNSs/C catalyst shows mass activity and specific activity at 0.90 V, surpassing those of commercial Pt/C catalyst by factors of 2.7 and 5.8, respectively, while also exhibiting superior stability. More importantly, the H2-O2 PEMFC with a P-PtNSs/C cathode exhibits higher current and power densities than one with Pt/C throughout the entire evaluation process, achieving a peak power density of 1.28 W cm−2 at a low Pt loading of 0.1 mgPt cm−2. This study will provide valuable insights into the nonmetals alloying and nanostructuring of Pt-based ORR electrocatalysts.

Extended H-bonds/π-bonds networks for boosting electron transfer over polydopamine-covered nanocellulose/g-C3N4 toward efficient photocatalytic H2O2 production

Photocatalytic hydrogen peroxide production (PHP) from H2O and O2 is a promising solar-to-chemical conversion technology. However, conventional doping, heterojunction and defect engineering of catalyst modification for enhanced PHP process is unable to meet the highly requirements of efficient oxygen reduction reaction (ORR), while also damaging the intrinsic crystal structure of the catalysts. Herein, we demonstrate a rationally extended H-bonds/π-bonds intermolecular networks between carbon nitride (g-C3N4, CN) and carboxylated cellulose nanofibers (CNF) with a small quantity of polydopamine (PDA) for solar H2O2 production. Ultimately, CN/CNFP exhibits an extraordinary PHP of 130.7 μmol·L−1·h−1, surpassing CN/CNF (75.2 μmol·L−1·h−1) and pure CN (20.1 μmol·L−1·h−1). Experimental and density function theory (DFT) have validated that CNFP increases the adsorption capabilities of O2, enhancing the efficiency of photogenerated charge transfer and separation via multiple hydrogen bonding/π-π stacking with g-C3N4, thereby facilitating the superior PHP via a two-step single-electron ORR pathway. This work offered a viable route to modulate directed transfer of photogenerated charges with multiple intermolecular interactions and presented an encouraging strategy to obtain high-efficient PHP.

High-Density CoSe2 Sites Embedded within 2D Porous N-Doped Carbon for High-Performance Oxygen Reduction Reaction Electrocatalysis.

Designing and fabricating efficient and stable nonprecious metal-based oxygen reduction reaction (ORR) electrocatalysts is a pressing and challenging task for the pursuit of sustainable new energy devices. Herein, porous P-CoSe2@NC electrocatalysts with high-density carbon-coated CoSe2 sites were successfully fabricated based on a pyridyl-porphyrinic metal-organic framework (Co-TPyP MOF) via a molten salt-assisted synthesis method. The hierarchical pore and N-doping carbon substrate of P-CoSe2@NC promotes mass transfer and electron-transfer efficiency, which is beneficial to maximize CoSe2 site utilization. Well-designed P-CoSe2@NC exhibits efficient ORR catalytic activity with a high half-wave potential of 0.863 V and excellent catalytic stability. Meanwhile, rechargeable aqueous primary/quasi-solid-state ZABs based on a P-CoSe2@NC air cathode show a high peak power density and exceptional operating stability, catering to the demands of practical applications. The qualified performance and structure stability of the electrocatalytic system may be mainly attributed to the protection of the CoSe2 nanoparticle by the coated carbon layer. Given the rational design of the structure and the component of the electrocatalyst with enhanced ORR activity, we believe that this work has provided a reliable pathway to the development of high-performance transition-metal chalcogenides for energy-storage and -conversion devices.

Highly dispersed Zn-N, S co-doped carbon for highly efficient electrocatalytic oxygen reduction

Supportive atomic Zn electrocatalysts exhibit excellent stability for oxygen reduction reaction (ORR) due to their fully occupied d orbitals of Zn, but their catalytic activity is not satisfactory. Whereas heteroatom doping can anchor the Zn atoms to achieve higher Zn loading; and additionally serve as auxiliary sites to enhance the catalytic activity of Zn sites. Herein, we present a method for the synthesis of N, S co-doped carbon with highly dispersed Zn (named Zn-NSC). The ORR activity of the Zn-NSC catalysts is optimized by adjusting the pyrolysis temperature and the atomic structure of the dopant molecules. The optimized Zn-NSC demonstrates significantly enhanced ORR electrocatalytic activity, this is attributable to its highly co-doping of N and S heteroatoms that are adjacent to Zn atoms. Specifically, the Zn-NSC3 catalyst exhibits remarkable ORR characteristics with excellent onset voltage (0.97 V vs RHE) and half-wave potential (0.87 V vs RHE), surpassing those of Pt/C (0.97 V and 0.85 V, respectively). Additionally, the Zn-NSC3 can be utilized as efficient cathode for Al-air batteries, achieving a high power density of 119.4 mW cm−2 and satisfactory discharge stability. This work proposes an approach for synthesizing low-cost and efficient ORR electrocatalysts for Al-air battery applications.

General Pyrolysis for High-Loading Transition Metal Single Atoms on 2D-Nitro-Oxygeneous Carbon as Efficient ORR Electrocatalysts.

Single-atom catalysts (SACs) possess the potential to involve the merits of both homogeneous and heterogeneous catalysts altogether and thus have gained considerable attention. However, the large-scale synthesis of SACs with rich isolate-metal sites by simple and low-cost strategies has remained challenging. In this work, we report a facile one-step pyrolysis that automatically produces SACs with high metal loading (5.2-15.9 wt %) supported on two-dimensional nitro-oxygenated carbon (M1-2D-NOC) without using any solvents and sacrificial templates. The method is also generic to various transition metals and can be scaled up to several grams based on the capacity of the containers and furnaces. The high density of active sites with N/O coordination geometry endows them with impressive catalytic activities and stability, as demonstrated in the oxygen reduction reaction (ORR). For example, Fe1-2D-NOC exhibits an onset potential of 0.985 V vs RHE, a half-wave potential of 0.826 V, and a Tafel slope of -40.860 mV/dec. Combining the theoretical and experimental studies, the high ORR activity could be attributed its unique FeO-N3O structure, which facilitates effective charge transfer between the surface and the intermediates along the reaction, and uniform dispersion of this active site on thin 2D nanocarbon supports that maximize the exposure to the reactants.

Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER) of 0.44 V and overpotentials for ORR (ηORR) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

Cobalt nanoparticles supported on nitrogen-doped carbon nanotubes for the efficient oxygen reduction reaction in Mg-air battery

Fabricating the non-precious-metal catalyst with desirable catalytic performance towards oxygen reduction reaction (ORR) is essential for Mg-air battery that adopts neutral brine electrolyte. However, the classic metal-nitrogen-carbon materials with strong ORR catalytic activity in alkaline solution usually display inferior performance than platinum-based catalysts in neutral environment. Herein, we construct a hybrid catalyst composed of cobalt nanoparticles and nitrogen-doped carbon nanotubes, based on pyrolyzing the mixture of melamine, pyrazole, hexadecyl trimethyl ammonium bromide, and 2-methylimidazole chelated with Co2+ and Zn2+ ions. This catalyst possesses abundant ORR catalytic active sites and mesoporous structure with large pore volume, which can result in the superior performance of Mg-air battery than that using Pt/C catalyst. Furthermore, its ORR catalytic mechanism is unraveled according to microstructure characterization and electrochemical response.

ZIF67-ZIF8@MFC-Derived Co-Zn/NC Interconnected Frameworks Combined with Perfluorosulfonic Acid Polymer as a Highly Efficient and Stable Composite Electrocatalyst for Oxygen Reduction Reactions.

The development of precious metal-free (M-N-C) catalysts for the oxygen reduction reaction (ORR) is considered crucial for reducing fuel cell costs. Herein, Co-Zn/NC interconnected frameworks with uniformly dispersed Co nanoparticles and graphitic carbon are designed and successfully synthesized through the in situ growth of zeolitic imidazolate frameworks (ZIF67 and ZIF8) along with biomass nano-microfibrillar cellulose (MFC), followed by pyrolysis. A Co-Zn/NC composite is prepared by combining Co-Zn/NC with a perfluorosulfonic acid polymer. The Co-Zn/NC composite catalyst exhibits excellent ORR catalytic activity (E0 = 0.974 V vs. RHE, E1/2 = 0.858 V vs. RHE) and good long-term durability, with 90% current retention after 10000s, surpassing that of commercial Pt/C in alkaline media. The hierarchical porous structure, coupled with the uniform distribution of Co nanoparticles and nitrogen doping, contributes to superior electrocatalytic performance, while the interconnected frameworks and graphitic carbon ensure good stability. Additionally, the Co-Zn/NC composite demonstrates promising applications in acidic media. This strategy offers significant guidance to develop advanced non-precious metal carbon-based catalysts for highly efficient and stable ORR.

Atomically dispersed Fe-N-C catalyst with densely exposed Fe-N4 active sites for enhanced oxygen reduction reaction

Atomically dispersed Fe-N-C catalysts are a promising alternative to platinum group metal (PGM) catalysts for oxygen reduction reaction (ORR). However, attaining efficient ORR activity and superior stability in Fe-N-C catalysts is still crucial yet challenging. Herein, we report a rational SiO2-mediated two-step pyrolysis strategy for stabilizing densely exposed Fe-N4 active sites on hierarchically porous carbon (HP-Fe-N-C/2). Benefiting from the high density of accessible Fe-N4 sites and the high graphitization degree of carbon support, the obtained HP-Fe-N-C/2 catalyst demonstrates outstanding activity and stability for ORR in both alkaline and acidic media. When used as the cathode catalyst, the assembled Zn-air battery shows a high peak power density of 217 mW cm−2 and ultra-long cycling stability for 1342 h without noticeable degradation. As a PGM-free cathode in proton exchange membrane fuel cells, it delivers a maximum output power density of 0.66 W cm−2.

N-Decorated Main-Group MgAl2O4 Spinel: Unlocking Exceptional Oxygen Reduction Activity for Zn-Air Batteries.

The development of economical and efficient oxygen reduction reaction (ORR) catalysts is crucial to accelerate the widespread application rhythm of aqueous rechargeable zinc-air batteries (ZABs). Here, a strategy is reported that the modification of the binding energy for reaction intermediates by the axial N-group converts the inactive spinel MgAl2O4 into the active motif of MgAl2O4-N. It is found that the introduction of N species can effectively optimize the electronic configuration of MgAl2O4, thereby significantly reducing the adsorption strength of *OH and boosting the reaction process. This main-group MgAl2O4-N catalyst exhibits a high ORR activity in a broad pH range from acidic and alkaline environments. The aqueous ZABs assembled with MgAl2O4-N shows a peak power density of 158.5mWcm-2, the long-term cyclability over 2000h and the high stability in the temperature range from -10 to 50°C, outperforming the commercial Pt/C in terms of activity and stability. This work not only serves as a significant candidate for the robust ORR electrocatalysts of aqueous ZABs, but also paves a new route for the effective reutilization of waste Mg alloys.

Electrochemically assisted polymerization synthesis of ZIF-derived Fe-N/C with high oxygen reduction reaction activity

Abstract The zeolitic imidazolate framework-8 (ZIF-8)-derived Fe-N/C catalysts show excellent oxygen reduction reactions (ORR) performance, but the harsh synthesis conditions and low yields have greatly limited their commercialization. Herein, we report an electrochemical-assisted polymerization method to produce a Fe-N/C structure (EC-Fe-N/C) with a high surface area (954.583 m2 g−1), high dispersion of Fe (2.2 wt %), and abundant N (2.05 wt %). The hierarchical structure exhibits excellent ORR activity (half-wave potential 0.88 V, in alkaline media) and outstanding zinc-air battery performance (energy density 821.3 mAh g−1 Zn, specific capacity 1017.1 Wh kg−1 Zn). This work may provide a simple and effective strategy to rationally design the Fe-N/C porous structure for highly efficient ORR activity.

Engineering ORR Electrocatalysts from Co8Pt4 Carbonyl Clusters via ZIF‐8 Templating

AbstractTo reduce the costs of proton exchange membrane fuel cells, the amount of Pt necessary to drive efficient oxygen reduction reaction (ORR) should be minimized. Particle nanostructuring, (nano‐)alloying, and metal‐doping can yield higher activities per Pt mass through tailoring catalysts owning a high number of active sites and precise electronic properties. In this work, the atom‐precise [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) cluster is encapsulated and activated in a zeolitic imidazolate framework (ZIF)‐8, which unlocks the access to defined, bare Pt−Co nanoclusters, Co8±xPt4±yNC@ZIF‐8, for the fabrication of highly active ORR catalysts. Upon controlled C‐interfacing and ZIF‐8‐digestion, Co‐doped Pt NPs (Pt27Co1) with a homogenous and narrow size distribution of (1.1±0.4) nm are produced on Vulcan® carbon. Restructuring of the Pt27Co1/C catalyst throughout the ORR measurement was monitored via high‐angle annular dark field‐scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The measured ORR mass activity of (0.42±0.07) A mgPt−1 and the specific activity of (0.67±0.06) mA cmECSA−2 compare favourably with the catalyst obtained by direct C‐interfacing the pristine Co8Pt4 cluster and with state‐of‐the‐art Pt/C reference catalysts. Our results demonstrate the potential of ZIF‐8‐mediated Pt−Co NP synthesis toward devising ORR catalysts with high Pt‐mass activity.

Tuning the Pyridine Units in Vinylene-Linked Covalent Organic Frameworks Boosting 2e- Oxygen Reduction Reaction.

The N-doped carbon materials are supposed to be the efficient oxygen reduction reaction (ORR) catalysts with the undefined N-doped carbon ring groups. It is essential to well define the role of the nitrogen atoms of these carbon structures in active behavior. Even though, the covalent organic frameworks (COFs) with precise structures are well developed, but unable to exclude the polar linkages influence. This study presents a series of pyridine-containing COFs linked via nonpolar carbon-carbon double bonds (C = C). Their catalytic activity and selectivity for 2e- ORR are successfully modulated by locating the embedded pyridine nitrogen in the backbones through the linking modes of pyridine moieties within the frameworks. Such phenomena can be attributed to their different binding abilities toward O2, leading to the different binding strength of the intermediate OH* to the catalytic sites, also verified by the theoretical calculation. This work provides us a new insight to design high-efficiency ORR catalysts through the exact location of pyridine nitrogen.

Light-Induced Variation of Lithium Coordination Environment in g-C3N4 Nanosheet for Highly Efficient Oxygen Reduction Reactions.

The structure and electronic state of the active center in a single-atom catalyst undergo noticeable changes during a dynamic catalytic process. The metal atom active center is not well demonstrated in a dynamic manner. This study demonstrated that Li metal atoms, serving as active centers, can migrate on a C3N4 monolayer or between C3N4 monolayers when exposed to light irradiation. This migration alters the local coordination environment of Li in the C3N4 nanosheets, leading to a significant enhancement in photocatalytic activity. The photocatalytic H2O2 process could be maintained for 35 h with a 920 mmol/g record-high yield, corresponding to a 0.4% H2O2 concentration, which is far greater than the value (0.1%) of practical application for wastewater treatment. Density functional theory calculations indicated that dynamic Li-coordinated structures contributed to the superhigh photocatalytic activity.

Dual-axial engineering on atomically dispersed catalysts for ultrastable oxygen reduction in acidic and alkaline solutions

Atomically dispersed catalysts are a promising alternative to platinum group metal catalysts for catalyzing the oxygen reduction reaction (ORR), while limited durability during the electrocatalytic process severely restricts their practical application. Here, we report an atomically dispersed Co-doped carbon-nitrogen bilayer catalyst with unique dual-axial Co-C bonds (denoted as Co/DACN) by a smart phenyl-carbon-induced strategy, realizing highly efficient electrocatalytic ORR in both alkaline and acidic media. The corresponding half-wave potential for ORR is up to 0.85 and 0.77 V (vs. reversible hydrogen electrode (RHE)) in 0.5 M H2SO4 and 0.1 M KOH, respectively, representing the best ORR activity among all non-noble metal catalysts reported to date. Impressively, the Zn-air battery (ZAB) equipped with Co/DACN cathode achieves outstanding durability after 1,688 h operation at 10 mA cm-2 with a high current density (154.2 mA cm-2) and a peak power density (210.1 mW cm-2). Density functional theory calculations reveal that the unique dual-axial cross-linking Co-C bonds of Co/DACN significantly enhance the stability during ORR and also facilitate the 4e- ORR pathway by forming a joint electron pool due to the improved interlayer electron mobility. We believe that axial engineering opens a broad avenue to develop high-performance heterogeneous electrocatalysts for advanced energy conversion and storage.

Asymmetric Atomic Tin Catalysts with Tailored p‐Orbital Electron Structure for Ultra‐Efficient Oxygen Reduction

AbstractAtomically dispersed transition metal–nitrogen–carbon (M–N–C) catalysts guide by the d‐band center theory have been extensively studied for oxygen reduction reaction (ORR) in various energy conversion and storage processes. However, asymmetric p‐block metal single‐atom catalysts (SACs) toward ORR have rarely been reported, and the origin of their catalytic activity is still unclear. Here, an asymmetric N, O coordinated Sn SAC is developed as an efficient ORR electrocatalyst. Remarkably, the optimized Sn SAC (e.g., Sn–N/O–C) exhibit outstanding ORR performance with a half‐wave potential of 0.910 V in alkaline media, outperforming most state‐of‐the‐art ORR catalysts. More importantly, the Sn–N/O–C possesses a long‐term durability in both alkaline and acidic electrolytes. Besides, Zn–air batteries based on the Sn–N/O–C cathode also show a higher energy density (254 mW cm‐2) than that of their reported M–N–C counterparts. Theoretical calculations suggest that the asymmetric N, O coordinated atomic Sn sites have a stronger binding interaction with O2 and better charge transfer ability compared with the symmetric SnN4 sites, thereby facilitating the ORR process. This work provides a nitrogen‐, oxygen‐coordinated engineering strategy for the rational design of highly active and durable carbon‐based catalysts with atomic p‐block metal sites for ORR and beyond.