Single-atom Sites Research Articles

Synergy of atomically dispersed Co–Fe pairs in nano-confined catalytic membranes enabling efficient water purification

Membrane-confined catalysis technologies have demonstrated the promise for continuous and efficient catalytic generation of reactive oxygen species (ROSs) to degrade organic pollutants. However, constructing improved membranes with feasible sub-/nanometer-confined spaces, adequate catalytic activity, and superior stability remains a major challenge for practical applications. Herein, we report the demonstration of a nano-confined catalytic membrane (CoFe-DSAC@GO) composed of bimetallic Co–Fe single-atoms anchored on nitrogen-doped carbon nanosheets and graphene oxide. The CoFe-DSAC@GO membrane exhibits 100 % removal efficiency with high water permeance (137 L m−2 h−1 bar−1), rapid degradation kinetics (0.41 ms–1), and excellent catalytic stability over 72 h. The nano-confined spaces in the CoFe-DSAC@GO membrane facilitate the generation and utilization of ROSs and catalytic activity. Furthermore, theoretical calculations elucidate that the electron transfer among bimetallic Co–Fe single-atom sites promotes peroxymonosulfate (PMS) activation. This work advances the mechanistic understanding and application potential of diatomic synergy in membrane-based nano-confined catalysis for water purification.

Heterogeneous Fe-Ni dual-atom catalysts coupled N-vacancy engineering for enhanced activation of peroxymonosulfate

The integration of nitrogen vacancies (Nv) exhibits significant role in promoting the efficiency of single-atom catalysts (SACs). Herein, a novel dual SAC, FeNi-Nv/CN, was developed via immobilizing Fe-Ni dual atoms onto graphitic carbon nitride with Nv sites. The FeNi-Nv/CN could effectively activate peroxymonosulfate (PMS) and generate plentiful reactive oxygen owing to the excellent Fenton-like catalytic property of FeNi, which could facilitate the degradation of Orange II. Moreover, the Nv in FeNi-Nv/CN could augment electron density around Fe-Ni atomic pairs obviously, which was beneficial to strengthen the electron transfer process (ETP) and further improve the degradation efficiency of Orange II. The density functional theory (DFT) calculations and experimental results of FeNi-Nv/CN testified the robust synergistic capacity between dual single-atomic reaction sites and Nv. This work provided a valuable strategy for the construction of dual SAC and could be a promising candidate in the effective degradation of environmental contaminant.

A General Strategy Based on Hetero-Charge Coupling Effect for Constructing Single-Atom Sites.

Single-atom catalysts have emerged as cutting-edge hotspots in the field of material science owing to their excellent catalytic performance brought about by well-defined metal single-atom sites (M SASs). However, huge challenges still lie in achieving the rational design and precise synthesis of M SASs. Herein, we report a novel synthesis strategy based on the hetero-charge coupling effect (HCCE) to prepare M SASs loaded on N and S co-doped porous carbon (M1/NSC). The proposed strategy was widely applied to prepare 17 types of M1/NSC composed of single or multi-metal with the integrated regulation of the coordination environment and electronic structure, exhibiting good universality and flexible adjustability. Furthermore, this strategy provided a low-cost method of efficiently synthesizing M1/NSC with high yields, that can produce more than 50 g catalyst at one time, which is key to large-scale production. Among various as-prepared unary M1/NSC (M can be Fe, Co, Ni, V, Cr, Mn, Mo, Pd, W, Re, Ir, Pt, or Bi) catalysts, Fe1/NSC delivered excellent performance for electrocatalytic nitrate reduction to NH3 with high NH3 Faradaic efficiency of 86.6 % and high NH3 yield rate of 1.50 mg h-1 mgcat. -1 at -0.6 V vs. RHE. Even using Fe1/NSC as a cathode in a Zn-nitrate battery, it exhibited a high open circuit voltage of 1.756 V and high energy density of 4.42 mW cm-2 with good cycling stability.

Capturing low-concentration benzene: Design and mechanism of high-performance Cu1-Ox,Ny-C single-atom adsorbents

Common adsorbents, such as active carbons, zeolites, and metal–organic frameworks (MOFs), struggle to capture low concentrations of benzene. Single-atom adsorbents (SAAs), boasting exceptional atomic utilization efficiency and precisely tailored electronic structures, offer a promising solution. This study first designed Cu1-Ox,Ny-C SAAs and explored their enhanced benzene adsorption through density functional theory (DFT). Particularly, a crucial link between the SA coordination configuration and its affinity for benzene was established. Next, Cu1-Ox,Ny-C was synthesized from the MOF MIL-101(Cr) and extensively characterized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, etc. to determine the coordination configuration of Cu single atoms. Finally, a thorough evaluation of the Cu1-Ox,Ny-C’ capacity and stability was conducted. Theoretical analysis revealed that Cu single atoms within the Ox,Ny-C matrix act as the primary adsorption sites for benzene. Notably, O and N atoms work synergistically: oxygen atoms promote adsorption, while nitrogen atoms mainly stabilize single-atom sites. Cu1-Ox,Ny-C was successfully synthesized, and characterization revealed that Cu1-O2,N2(trans)-C and Cu1-O3,N1-C were the dominant coordination configurations. Remarkably, despite a fourfold decrease in specific surface area compared to MIL-101(Cr), Cu1-Ox,Ny-C exhibited a threefold increase in chemisorption capacity for low-concentration benzene. Moreover, it exhibits excellent resistance to H2O and can be effectively reused. This study demonstrates a valuable strategy for designing and creating highly efficient SAAs for capturing low concentrations of benzene.

Anchoring Pt single atoms on specific nitrogen vacancies of carbon nitride to accelerate photogenerated carrier transfer

The anchoring sites of metal single atoms are closely related to photogenerated carrier dynamics and surface reactions. Achieving smooth photogenerated charge transfer through precise design of single-atom anchoring sites is an effective strategy to enhance the activity of photocatalytic hydrogen evolution. In this study, Pt single atoms were loaded onto ultra-thin carbon nitride with two-coordination nitrogen vacancies (VN2c-UCN-Pt) and ultra-thin carbon nitride with three-coordination nitrogen vacancies (VN3c-UCN-Pt). This paper investigated the photocatalytic hydrogen evolution performance and photogenerated carrier behavior of Pt single atoms at different anchoring sites. Surface photovoltage measurements indicated that VN2c-UCN-Pt exhibits a superior carrier separation efficiency compared to VN3c-UCN-Pt. More importantly, the surface photovoltage signal under the presence of H2O molecules revealed a significant decrease. Theoretical calculations suggest that VN2c-UCN-Pt exhibits superior capabilities in adsorbing and activating H2O molecules. Consequently, the photocatalytic hydrogen evolution efficiency of VN2c-UCN-Pt reaches 1774 µmol g−1h−1, which is 1.8 times that of VN3c-UCN-Pt with the same Pt loading. This work emphasized the structure–activity relationship between single-atom anchoring sites and photocatalytic activity, providing a new perspective for designing precisely dispersed single-atom sites to achieve efficient photocatalytic hydrogen evolution.

Electron Donor–Acceptor Activated Single Atomic Sites for Boosting Oxygen Reduction Reaction

AbstractFabricating efficient non‐platinum‐group‐metal catalysts for the oxygen reduction reaction (ORR) in proton‐exchange membrane fuel cells still remains a big challenge. This study creates a unique bamboo‐like architecture of Mn and Fe single atomic sites (SASs) anchored on core‐shell structure of nanopaticles@carbon nanotubes (MnFe SASs/NPs@CNTs) via a precursor route, where the Fe nanoparticles (NPs) (identified as γ‐Fe and Austenite) are confined into CNTs, such an architecture exhibits compelling ORR activity and durability in 0.1 m HClO4. Experiments and calculations both reveal that the electron donor–acceptor paradigm between Mn SASs and Fe NPs launches a lattice‐electron coupling mechanism not only increasing occupation of π‐antibonding orbital in Mn−*O intermediates but also rising Jahn–Teller effect, thereby destabilize the Mn−*O intermediate and eventually facilitate the potential‐limiting step from *O to *OH. Such a coupling activation of the ORR‐inert Mn SASs greatly improves ORR performances of MnFe SASs/NPs@CNTs.

Fe based MOF encapsulating triethylenediamine cobalt complex to prepare a FeN3-CoN3 dual-atom catalyst for efficient ORR in Zn-air batteries

Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.

Reversible metal cluster formation on Nitrogen-doped carbon controlling electrocatalyst particle size with subnanometer accuracy

Copper and nitrogen co-doped carbon catalysts exhibit a remarkable behavior during the electrocatalytic CO2 reduction (CO2RR), namely, the formation of metal nanoparticles from Cu single atoms, and their subsequent reversible redispersion. Here we show that the switchable nature of these species holds the key for the on-demand control over the distribution of CO2RR products, a lack of which has thus far hindered the wide-spread practical adoption of CO2RR. By intermitting pulses of a working cathodic potential with pulses of anodic potential, we were able to achieve a controlled fragmentation of the Cu particles and partial regeneration of single atom sites. By tuning the pulse durations, and by tracking the catalyst’s evolution using operando quick X-ray absorption spectroscopy, the speciation of the catalyst can be steered toward single atom sites, ultrasmall metal clusters or large metal nanoparticles, each exhibiting unique CO2RR functionalities.

Carbon-Boosted and Nitrogen-Stabilized Isolated Single-Atom Sites for Direct Dehydrogenation of Lower Alkanes.

Lower olefins are widely used in the chemical industry as basic carbon-based feedstocks. Here, we report the catalytic system featuring isolated single-atom sites of iridium (Ir1) that can function within the entire temperature range of 300-600 °C and transform alkanes with conversions close to thermodynamics-dictated levels. The high turnover frequency values of the Ir1 system are comparable to those of homogeneous catalytic reactions. Experimental data and theoretical calculations both indicate that Ir1 is the primary catalytic site, while the coordinating C and N atoms help to enhance the activity and stability, respectively; all three kinds of elements cooperatively contribute to the high performance of this novel active site. We have further immobilized this catalyst on particulate Al2O3, and we found that the resulting composite system under mimicked industrial conditions could still give high catalytic performances; in addition, we have also developed and established a new scheme of periodical in situ regeneration specifically for this composite particulate catalyst.

Cooperative dual single atom Ni/Cu catalyst for highly selective CO2-to-ethanol reduction

The electrochemical CO2-to-ethanol conversion bargains a promising approach to lowering CO2 emission while yielding valuable chemical products. Here, we report the NiCu-SACs/N-C catalysts with cooperative dual heteroactive sites that achieve by far the highest catalytic activity for yielding ethanol with the unprecedented Faradaic efficiency of 92.2 % at the potential of −0.6 V versus RHE. The catalyst exhibits the lowest onset potential of −0.4 V versus RHE to catalyze CO2-to-ethanol conversion. In-operando X-ray absorption spectroscopy provides an interesting observation of restructuring behavior of dynamically generated Cu clusters from atomically distributed Cu single-atoms and reversible structural changes or oxidation states of Cu sites while Ni sites remain unchanged during the catalytic reactions. Our experimental analysis and DFT computation suggest that CO produced on Cu-N4/Ni-N3 cooperative single atom sites undergoes C-C coupling, which is further reduced into ethanol. This strategy provides a new route to design selective and efficient catalysts for CO2-to-ethanol conversion.

Breaking scaling relation of single-atom site via energy storage-release effect from adjacent carbon vacancy for low-temperature-resistant Fenton-like catalysis

To realize efficient antibiotics degradation in low-temperature water, single-atom FeN4 sites are engineered near carbon vacancies in a porous catalyst (PCvFe1-5) via thermal-etching and pyrolysis. The high-specific-surface-area (2202.80 m2 g−1) carbon support and dispersive Fe atoms co-enrich sulfamethoxazole and peroxymonosulfate to enhance the reactant collision frequency. Carbon vacancies allow the catalyst to deform for storing the peroxymonosulfate adsorption energies at FeN4 sites, which are subsequently released to facilitate -SO4H desorption for rapid site regeneration. This breaks the scaling relation suffered by single-atom sites, thereby reducing the thermodynamic energy barrier. Consequently, a low-temperature-resistant Fenton-like system with ultralow activation energy of 9.06 kJ mol−1 is constructed for sulfamethoxazole degradation. The normalized kinetic rate constant at 2 ℃ exceeds that of reported catalysts working at 25/30 ℃ by 1–2 orders of magnitude. Moreover, due to the special site configuration, PCvFe1-5 degrades sulfamethoxazole via both long-range catalyst-mediated electron transfer and short-range direct collision oxidation.

One single-atom Mn doping strategy enabling two functions of oxygen reduction reaction and pseudocapacitive performance

Single-atom metal species as highly effective active sites are crucial for enhancing energy storage and conversion properties. However, achieving the simultaneous construction of single-atom sites and the regulation of matrix structures to enable their application in both energy storage and conversion remains a challenge. Here, we have successfully developed unique MnN2C2 active sites, atomically dispersed on N-doped mesoporous graphitic carbon sheets (MnSAs/NMC). This is accomplished through the strategic utilization of MnCl2 salt, which serves dual roles of a pore-forming agent and a template. The MnSAs/NMC catalyst demonstrates compelling electrocatalytic activity for the oxygen reduction reaction (ORR), with an impressive half-wave potential (E1/2 = 0.90 V), alongside superior capacitance reaching 444 F g-1 at 0.5 A g-1 for supercapacitors. Crucially, both experimental and theoretical simulations validate that the single-atom dispersed MnN2C2 optimizes the adsorption energy of reactants and intermediates in the ORR process and pseudocapacitive behavior, leading to excellent ORR activity and capacitive performance. Interestingly, MnSAs/NMC-based Zn-air batteries exhibit concurrently high-power density derived from capacitive property and high energy density enhanced by ORR process. This study presents a novel preparation method for single-atom catalysts, which paves the way for the commercial application of super energy storage and conversion devices.

Atomic-Level Asymmetric Tuning of the Co1-N3P1 Catalyst for Highly Efficient N-Alkylation of Amines with Alcohols.

Despite the extensive development of non-noble metals for the N-alkylation of amines with alcohols, the exploitation of catalysts with high selectivity, activity, and stability still faces challenges. The controllable modification of single-atom sites through asymmetric coordination with a second heteroatom offers new opportunities for enhancing the intrinsic activity of transition metal single-atom catalysts. Here, we prepared the asymmetric N/P hybrid coordination of single-atom Co1-N3P1 by absorbing the Co-P complex on ZIF-8 using a concise impregnation-pyrolysis process. The catalyst exhibits ultrahigh activity and selectivity in the N-alkylation of aniline and benzyl alcohol, achieving a turnover number (TON) value of 3480 and a turnover frequency (TOF) value of 174-h. The TON value is 1 order of magnitude higher than the reported catalysts and even 37-fold higher than that of the homogeneous catalyst CoCl2(PPh3)2. Furthermore, the catalyst maintains its high activity and selectivity even after 6 cycles of usage. Controlling experiments and isotope labeling experiments confirm that in the asymmetric Co1-N3P1 system, the N-alkylation of aniline with benzyl alcohol proceeds via a transfer hydrogenation mechanism involving the monohydride route. Theoretical calculations prove that the superior activity of asymmetric Co1-N3P1 is attributed to the higher d-band energy level of Co sites, which leads to a more stable four-membered ring transition state and a lower reaction energy barrier compared to symmetrical Co1-N4.

Engineering Single-Atom Sites with the Irving-Williams Series for the Simultaneous Co-photocatalytic CO2 Reduction and CH3CHO Oxidation.

The bonding effects between 3d transition-metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition-metal atoms of the spontaneous geometrical distortions, that is the Jahn-Teller effect, can alter CFSE, thereby leading to the Irving-Williams series. However, engineering single-atom sites (SASs) using the Irving-Williams series as an ideal guideline has not been reported to date. Herein, alkynyl-linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving-Williams series was employed to accurately predict the bonding effects between 3d transition-metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu-SASs/CPFs exhibits higher stability and faster charge-transfer efficiency, far surpassing other metal-SASs/CPFs. As expected, Cu-SASs/CPFs demonstrates a high photoreduction of CO2-to-CO activity (~30.3 μmol ⋅ g-1 ⋅ h-1) and an exceptional photooxidation of CH3CHO-to-CH3COOH activity (~24.7 μmol ⋅ g-1 ⋅ h-1). Interestingly, the generated *O2 - is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving-Williams to regulate the catalytic performances.

Engineering Single‐Atom Sites with the Irving–Williams Series for the Simultaneous Co‐photocatalytic CO2 Reduction and CH3CHO Oxidation

AbstractThe bonding effects between 3d transition‐metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition‐metal atoms of the spontaneous geometrical distortions, that is the Jahn–Teller effect, can alter CFSE, thereby leading to the Irving–Williams series. However, engineering single‐atom sites (SASs) using the Irving–Williams series as an ideal guideline has not been reported to date. Herein, alkynyl‐linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving–Williams series was employed to accurately predict the bonding effects between 3d transition‐metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu‐SASs/CPFs exhibits higher stability and faster charge‐transfer efficiency, far surpassing other metal‐SASs/CPFs. As expected, Cu‐SASs/CPFs demonstrates a high photoreduction of CO2‐to‐CO activity (~30.3 μmol ⋅ g−1 ⋅ h−1) and an exceptional photooxidation of CH3CHO‐to‐CH3COOH activity (~24.7 μmol ⋅ g−1 ⋅ h−1). Interestingly, the generated *O2− is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving–Williams to regulate the catalytic performances.

Single-Atom Catalysts through Pressure-Controlled Metal Diffusion.

Single-atom catalysts (SACs) open up new possibilities for advanced technologies. However, a major complication in preparing high-density single-atom sites is the aggregation of single atoms into clusters. This complication stems from the delicate balance between the diffusion and stabilization of metal atoms during pyrolysis. Here, we present pressure-controlled metal diffusion as a new concept for fabricating ultra-high-density SACs. Reducing the pressure inhibits aggregation substantially, resulting in almost three times higher single-atom loadings than those obtained at ambient pressure. Molecular dynamics and computational fluid dynamics simulations reveal the role of a metal hopping mechanism, maximizing the metal atom distribution through an increased probability of metal-ligand binding. The investigation of the active site density by electrocatalytic oxygen reduction validates the robustness of our approach. The first realization of Ullmann-type carbon-oxygen couplings catalyzed on single Cu sites demonstrates further options for efficient heterogeneous catalysis.

Introducing Hydrogen-Bonding Microenvironment in Close Proximity to Single-Atom Sites for Boosting Photocatalytic Hydrogen Production.

Inspired by enzymatic catalysis, it is crucial to construct hydrogen-bonding-rich microenvironment around catalytic sites; unfortunately, its precise construction and understanding how the distance between such microenvironment and catalytic sites affects the catalysis remain significantly challenging. In this work, a series of metal-organic framework (MOF)-based single-atom Ru1 catalysts, namely, Ru1/UiO-67-X (X = -H, -m-(NH2)2, -o-(NH2)2), have been synthesized, where the distance between the hydrogen-bonding microenvironment and Ru1 sites is modulated by altering the location of amino groups. The -NH2 group can form hydrogen bonds with H2O, constituting a unique microenvironment that causes an increased water concentration around the Ru1 sites. Remarkably, Ru1/UiO-67-o-(NH2)2 displays a superior photocatalytic hydrogen production rate, ∼4.6 and ∼146.6 times of Ru1/UiO-67-m-(NH2)2 and Ru1/UiO-67, respectively. Both experimental and computational results suggest that the close proximity of amino groups to the Ru1 sites in Ru1/UiO-67-o-(NH2)2 improves charge transfer and H2O dissociation, accounting for the promoted photocatalytic hydrogen production.

Efficient Electrosynthesis of Urea over Single-Atom Alloy with Electronic Metal Support Interaction.

Urea electrosynthesis from carbon dioxide (CO2) and nitrate (NO3 -) is an alternative approach to traditional energy-intensive urea synthesis technology. Herein, we report a CuAu single-atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 μg h-1 mgcat -1 at -0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at -0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single-atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C-N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C-N coupling at the atomic level, which can provide guidance for the development of C-N coupling systems.

Highly efficient recycling of polyester wastes to diols using Ru and Mo dual-atom catalyst

The chemical recycling of polyester wastes is of great significance for sustainable development, which also provides an opportunity to access various oxygen-containing chemicals, but generally suffers from low efficiency or separation difficulty. Herein, we report anatase TiO2 supported Ru and Mo dual-atom catalysts, which achieve transformation of various polyesters into corresponding diols in 100% selectivity via hydrolysis and subsequent hydrogenation in water under mild conditions (e.g., 160 °C, 4 MPa). Compelling evidence is provided for the coexistence of Ru single-atom and O-bridged Ru and Mo dual-atom sites within this kind of catalysts. It is verified that the Ru single-atom sites activate H2 for hydrogenation of carboxylic acid derived from polyester hydrolysis, and the O-bridged Ru and Mo dual-atom sites suppress hydrodeoxygenation of the resultant alcohols due to a high reaction energy barrier. Notably, this kind of dual-atom catalysts can be regenerated with high activity and stability. This work presents an effective way to reconstruct polyester wastes into valuable diols, which may have promising application potential.

Design of Atomically Dispersed CoN4 Sites and Co Clusters for Synergistically Enhanced Oxygen Reduction Electrocatalysis.

Constructing dual-site catalysts consisting of atomically dispersed metal single atoms and metal atomic clusters (MACs) is a promising approach to further boost the catalytic activity for oxygen reduction reaction (ORR). Herein, a porous CoSA-AC@SNC featuring the coexistence of Co single-atom sites (CoN4) and S-coordinated Co atomic clusters (SCo6) in S, N co-doped carbon substrate is successfully synthesized by using porphyrinic metal-organic framework (Co-TPyP MOF) as the precursor. The introduction of the sulfur source creates abundant microstructural defects to anchor Co metal clusters, thus modulating the electronic structure of its surrounding carbon substrate. The synergistic effect between the two types of active sites and structural advantages, in turn, results in high ORR performance of CoSA-AC@SNC with half-wave potential (E1/2) of 0.86V and Tafel slope of 50.17mVdec-1. Density functional theory (DFT) calculations also support the synergistic effect between CoN4 and SCo6 by detailing the catalytic mechanism for the improved ORR performance. The as-fabricated Zn-air battery (ZAB) using CoSA-AC@SNC demonstrates impressive peak power density of 174.1mWcm-2 and charge/discharge durability for 148h. This work provides a facile synthesis route for dual-site catalysts and can be extended to the development of other efficient atomically dispersed metal-based electrocatalysts.