Metal Sites Research Articles

A Multifunctional Na2Se/Zn-Mn Skeleton Enables Processable and Highly Reversible Sodium Metal Anode.

The recent high-energy density sodium (Na) metal batteries (SMBs) are restricted by their processability, lifetime, and safety. These issues can be addressed by controlling the reactions at the Na metal by modifying the Na metal anode (SMA) with the sodiophilic hosts. Herein, a multifunctional Na2Se/Zn-Mn skeleton is introduced for SMA and fabricate a processable Na@Na2Se/Zn-Mn composite using repeated cold rolling/folding approach through the spontaneous reaction between Na metal and ZnMnSe alloy. This unique intermetallic composite has Zn and Mn metal sites for uniform deposition of Na, while Na2Se generates a stable SEI for rapid Na+ ion transport. It offers outstanding sodiophilicity, high processability, excellent mechanical strength, and high ionic conductivity due to the synergistic effect of multi-component, enabling stable Na plating/stripping at high current densities and areal capacities. An optimized Na2Se/Zn-Mn skeleton enables Na||Na symmetric cells to attain a high critical current density of 5.0mA cm-2 at 5.0 mAh cm-2 with an extended lifespan of 9000h at 1.0mA cm-2 at 1.0 mAh cm-2. Remarkably, when configured into a full cell with a Na3V2(PO4)3 cathode, the SMB displays an extended lifespan of 2000 cycles at 10 C and an impressive high-rate capacity of ≈61.6 mAh g-¹ at 30 C.

Reconstructing the Coordination Environment of Fe/Co Dual-atom Sites towards Efficient Oxygen Electrocatalysis for Zn-Air Batteries.

Dual-atom catalysts with nitrogen-coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc-air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual-atom catalysts of FeCo-N-C can undergo out-plane and in-plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo-N-C with shortened Fe-N bonds also favor the ORR process, therefore is a promising dual-atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm-2, and exhibit no notable decline after ~ 720 h of continuous cycling.

Cell-Inspired Microreactor with Compartmentalized Active Sites for Development of Cascade Catalysis System in Biosensing.

Enzymatic cascade reactions with high activity and specificity in living cells always benefit from multicompartmentalized organelles that provide separately confined spaces for enzymes, avoiding their mutual interference to ensure the high-efficiency operation of necessary vital movements. Inspired by this, we designed a 3D spherical microreactor (Au@H-APF@Pt) with biomimetic cascade catalysis for glucose detection. First, ultrasmall gold nanoparticles were immobilized in situ on the internal cavities of hollow 3-aminophenol formaldehyde resin (H-APF) nanospheres, along with glucose oxidase activity. Then, platinum nanoparticles (PtNPs) with peroxide-like activity were reduced surrounding the outer layer of the H-APF nanospheres. Similar to the cell structure, different metal sites in this bifunctional microreactor operated independently, bringing higher catalytic activity and selectivity and thus being synergistically capable of a cascade reaction to catalyze the substrate for glucose detection. This cell-mimicking microreactor (Au@H-APF@Pt) was successfully applied in glucose colorimetric detection, showing a 1.9-fold activity enhancement compared to direct mixing (Au/Pt). The observed low catalytic activity was attributed to the extended time for transferring hydrogen peroxide (H2O2) from Au NPs to the solution and then to PtNPs. Integrating a smartphone APP, a real-time, visual, and Au@H-APF@Pt-based hydrogel sensor for glucose detection was also proposed. Satisfactory results highlight that this cell-mimicking microreactor offers a very successful strategy to improve the efficiency of cascade catalysis systems in biosensing.

Activating Oxygen via the 3‐Electron Pathway to Hydroxyl Radical by La‐O4 Single‐atom on WO3 for Water Purification

Shifting photocatalytic oxygen activation towards 3‐electron (e‐) pathway to hydroxyl radicals, instead of the normal 1 e‐ to superoxide radicals, becomes increasingly important for pollution degradation since hydroxyl radicals possess a high oxidation potential (2.80 V). Here, we demonstrate a selective oxygen activation to hydroxyl radicals via 3 e‐ pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La‐O coordination strength (denoted as LaO4‐WOv). Unsaturated‐state La overcomes the rate‐limited step of 2 e‐ oxygen reduction reaction towards to hydrogen peroxide via tuning binding free energy of key reaction intermediate *OOH, stepped by easy generation of hydroxyl radicals via 1 e‐. This strategy alters the activation of oxygen process from 1 e‐ to 3 e‐. Hydrogen peroxide and hydroxyl radicals over LaO4‐WOv produces 3.8 and 3.3 mmol L‐1 h‐1, 35 and 8 times that of detected over WO3, respectively. Rapid and complete removal of tetracycline realizes over LaO4‐WOv with 0.077 min‐1 of rate constant, 38 times that of WO3. Degradation efficiencies keep greater than 98% following five repeats, revealing a practical‐utilization‐level robust stability. This work builds an unsaturated‐state transition metal site for manipulating oxygen activation towards an effective water purification as a representative application.

Modulating Coordination Environment of Cobalt-Based Spinel Octahedral Metal Sites to Boost Metal–Oxygen Bond Covalency for Reversible Lithium–Oxygen Batteries

Modulating Coordination Environment of Cobalt-Based Spinel Octahedral Metal Sites to Boost Metal–Oxygen Bond Covalency for Reversible Lithium–Oxygen Batteries

High‐Throughput Screening of Dual‐Atom Catalysts for Methane Combustion: A Combined Density Functional Theory and Machine‐Learning Study

AbstractCeria‐supported precious metal catalysts have undergone extensive investigation for the catalytic methane combustion. However, it remains a significant challenge to achieve both highly synergistic oxidation activity and efficient atom utilization remains a challenge for commonly used supported nanoparticles and single‐atom catalysts. Dual‐atom catalysts (DACs) emerges as a frontier of advanced catalysts, presenting unique catalytic properties that benefit from the synergy of neighboring metal sites. In this study, 361 ceria‐supported DACs (M1M2/CeO2) encompassing combinations of 19 transition metals are systematically explored. Using high‐throughput density functional theory calculations, the structures, stability as well as activity of M1M2/CeO2 are assessed. Notably, Au1Ga1/CeO2 is identified as a promising DAC exhibiting high activity for methane total oxidation, substantiated by comprehensive DFT‐calculated reaction pathways. Furthermore, employing six machine‐learning algorithms, the structure‐properties relationship is explored within ceria‐based DACs and highlight the importance of oxidation states and atomic radii of doped metals as the descriptors. The trained model by computational dataset exhibits high accuracy and predict a more active Mn1Au1/CeO2 than those screened using only DFT datasets. The high‐throughput strategy demonstrated in this work not only provides insights into the rational design of methane oxidation catalysts, but also paves the way for exploring DACs for diverse applications.

Activating Oxygen via the 3-Electron Pathway to Hydroxyl Radical by La-O4 Single-atom on WO3 for Water Purification.

Shifting photocatalytic oxygen activation towards 3-electron (e-) pathway to hydroxyl radicals, instead of the normal 1 e- to superoxide radicals, becomes increasingly important for pollution degradation since hydroxyl radicals possess a high oxidation potential (2.80 V). Here, we demonstrate a selective oxygen activation to hydroxyl radicals via 3 e- pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La-O coordination strength (denoted as LaO4-WOv). Unsaturated-state La overcomes the rate-limited step of 2 e- oxygen reduction reaction towards to hydrogen peroxide via tuning binding free energy of key reaction intermediate *OOH, stepped by easy generation of hydroxyl radicals via 1 e-. This strategy alters the activation of oxygen process from 1 e- to 3 e-. Hydrogen peroxide and hydroxyl radicals over LaO4-WOv produces 3.8 and 3.3 mmol L-1 h-1, 35 and 8 times that of detected over WO3, respectively. Rapid and complete removal of tetracycline realizes over LaO4-WOv with 0.077 min-1 of rate constant, 38 times that of WO3. Degradation efficiencies keep greater than 98% following five repeats, revealing a practical-utilization-level robust stability. This work builds an unsaturated-state transition metal site for manipulating oxygen activation towards an effective water purification as a representative application.

Oxygen Plasma Triggered Co−O−Fe Motif in Prussian Blue Analogue for Efficient and Robust Alkaline Water Oxidation

AbstractIn the context of oxygen evolution reaction (OER), the construction of high‐valence transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high‐valence metal sites, particularly in high‐current‐density water‐splitting systems. Here, we have successfully constructed Co−O−Fe catalytic active motifs in cobalt‐iron Prussian blue analogs (CoFe‐PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability. Our spectroscopic and theoretical studies reveal that the Co−O−Fe bridged motifs enable a unique double‐exchange interaction between Co and Fe atoms, promoting the formation of high‐valence Co species as OER active centers while maintaining Fe in a low‐valence state, preventing its dissolution. The resultant catalyst (CoFe‐PBA‐30) requires an overpotential of only 276 mV to achieve 1000 mA cm−2. Furthermore, the assembled alkaline exchange membrane electrolyzer using CoFe‐PBA‐30 as anode material achieves a high current density of 1 A cm−2 at 1.76 V and continuously operates for 250 hours with negligible degradation. This work provides significant insights for activating lattice oxygen redox without compromising structure stability in practical water electrolyzers.

Strategy for Enhancing Catalytic Active Site: Introduction of 1D material InSeI for Electrochemical CO2 Reduction to Formate.

The presence of oxygen vacancies (Vo) in electrocatalysts plays a significant role in improving the selectivity and activity of CO2 reduction reaction (CO2RR). In this study, 1D material with large surface area is utilized to enable uniform Vo formation on the catalyst. 1D structured indium selenoiodide (InSeI) is synthesized and used as an electrocatalyst for the conversion of CO2 to formate. The electrochemical treatment of InSeI leads to the leaching of Se and I from the catalyst surface and the formation of Vo. The resulting Vo promotes the activity of the CO2RR, which increases the local pH of the catalyst surface and chemically maintains the oxidized metal sites on the catalyst. Owing to these characteristics, activated In wire exhibited remarkable CO2RR activity, thereby surpassing 93% FEformate at 500mA cm-2, with a maximum of 97.3% FEformate at 100mA cm-2. Moreover, the catalytic activity remained consistent for over 50h at 100mA cm-2 (FEformate >88%). Thus, the findings imply that using 1D materials can facilitate the formation of oxygen vacancies on the catalyst surface and improve the selectivity and durability of CO2RR. This indicates the potential for further research on 1D materials as electrocatalysts.

Chemically Modified HKUST-1(Cu) for Gas Adsorption and Separation: Mixed-Metal and Hierarchical Porosity.

The archetypical metal-organic framework (MOF), HKUST-1, has been systematically modified in both its organic and inorganic building blocks to introduce diversity in the metal centers and create defects within the network, achieving a variety of bimetallic hierarchical structures. These modifications changed the affinity of the MOFs for acid gases. The introduction of bimetallic sites mostly affects CO2 adsorption, while the hierarchical structure generates an increase in SO2 uptake capacity, allowing better performance in the separation of binary mixtures of these gases near room temperature. Notably, the synthesized HH-Cu100 material exhibited an exceptionally high IAST SO2/CO2 (10:90) selectivity of 3420 at 298 K, outperforming benchmark MOFs with open metal sites.

Metal-organic framework-based self-supported electrodes for oxygen evolution reaction

Oxygen evolution reactions (OER), commonly employed in applications such as metal-air batteries, water electrolysis, fuel cells, etc. , often suffer from slow kinetics, thus leading to ultra-high potentials that severely affect device energy efficiency. Metal-organic frameworks (MOFs) have garnered massive attention as electrodes for OER, benefiting from their highly ordered porous frameworks, abundant accessible active metal sites, and adjustable lattice structures. However, using powdered MOFs in OER poses a challenge, limiting the exposure of numerous active sites and resulting in suboptimal efficiency. To address this limitation, the trend towards designing MOF-based self-supported electrodes with enhanced contact between MOFs and the current collector has gained considerable attention for OER applications. This review highlights recent advancements and future prospects in developing MOF-based self-supported electrodes for OER. We delve into various aspects, including preparation methods, optimization strategies, catalytic efficiencies, and OER mechanisms with MOF-based electrocatalysts. Furthermore, we explore the existing challenges associated with MOF-based self-supported electrodes for OER. This comprehensive overview provides valuable insights into the evolving landscape of MOF-based materials in advancing OER.

Aldehyde Directed In Situ Loading of Ag Nanodots Around the Open Metal Sites of MOFs for the Tandem Catalysis of Nitrate to Ammonia.

Both spatial arrangement and intrinsic activity of electrocatalysts with dual-active sites are widely designed to match the coupling reaction between nitrate and water, in which most of the reactive intermediates can be optimized to achieve a high yield rate of ammonia. Herein, by introducing the aldehyde group inside metal-organic frameworks (MOFs) in advance, an aldehyde-induced method is achieved to direct the in situ nucleation of Ag nanodots depending on the mesopores of MOFs via a simple silver mirror reaction. The key point here is that the spatial arrangement between the aldehyde group and open metal sites is fixed end to end, which makes the aldehyde group a built-in redox-active site to drive the in situ nucleation of Ag nanodots next to the open metal sites of MOFs. Accordingly, by varying the metal sites of MOFs, a group of M-MOFs@Ag (M = Fe, Co, Ni, Cu, etc.) hybrids with dual active sites are acquired. Taking Ni-MOFs@Ag as an example, the interaction between Ni2+ and Ag sites makes it available for the tandem catalysis of nitrate-to-ammonia, in which the H· and NO2 - generated on the open Ni2+ sites and Ag nanodots, respectively, can migrate to each other to evolve into ammonia.

Electron‐Penetrating in Heterointerface Engineering for Oxygen Evolution Reaction in Seawater Splitting

AbstractThe interfacial electric field (IEF) between heterogeneous units plays an important role in the electronic modulation of active centers during oxygen evolution reaction (OER). However, the weak electronic coupling between spatially separated IEFs limits the deep activation of metal sites on the surface of the catalyst. Herein, a proof‐of‐concept strategy is provided that imbed MS2 (M = Ni3Fe) species with high spin Fe orbits into heterogeneous units to promote the electron penetrating between IEFs. By designing a Fe2O3@MS/MS2@MOy model catalyst, the electronic interaction between adjacent IEFs is effectively enhanced for the deep oxidation of bimetals on the surface, breaking the competing relationship between adsorbed evolution mechanism (AEM) and lattice oxygen mechanism (LOM) of catalysts during OER. As a result, the onset overpotential of the synthesized electrode is only 171 mV, and it maintains excellent stability for more than 2300 h at a current density of 10 mA cm−2 in 1 M KOH + 0.5 M NaCl electrolyte.

Tailoring d‐Band Center of Single‐Atom Nickel Sites for Boosted Photocatalytic Reduction of Diluted CO2 from Flue Gas

AbstractPhotocatalytic reduction of diluted CO2 from anthropogenic sources holds tremendous potential for achieving carbon neutrality, while the huge barrier to forming *COOH key intermediate considerably limits catalytic effectiveness. Herein, via coordination engineering of atomically scattered Ni sites in conductive metal–organic frameworks (CMOFs), we propose a facile strategy for tailoring the d‐band center of metal active sites towards high‐efficiency photoreduction of diluted CO2. Under visible‐light irradiation in pure CO2, CMOFs with Ni‐O4 sites (Ni‐O4 CMOFs) exhibits an outstanding rate for CO generation of 13.3 μmol h−1 with a selectivity of 94.5 %, which is almost double that of its isostructural counterpart with traditional Ni‐N4 sites (Ni‐N4 CMOFs), outperforming most reported systems under comparable conditions. Interestingly, in simulated flue gas, the CO selectivity of Ni‐N4 CMOFs decreases significantly while that of Ni‐O4 CMOFs is mostly unchanged, signifying the supremacy for Ni‐O4 CMOFs in leveraging anthropogenic diluted CO2. In situ spectroscopy and density functional theory (DFT) investigations demonstrate that O coordination can move the center of the Ni sites′ d‐band closer to the Fermi level, benefiting the generation of *COOH key intermediate as well as the desorption of *CO and hence leading to significantly boosted activity and selectivity for CO2‐to‐CO photoreduction.

Location-Specific Microenvironment Modulation Around Single-Atom Metal Sites in Metal-Organic Frameworks for Boosting Catalysis.

Despite coordination environment of catalytic metal sites has been recognized to be of great importance in single-atom catalysts (SACs), a significant challenge remains in the understanding how the location-specific microenvironment in the higher coordination sphere influences their catalysis. Herein, a series of Cu-based SACs, namely Cu1/UiO-66-X (X = -NO2, -H, and -NH2), are successfully constructed by anchoring single Cu atoms onto the Zr-oxo clusters of metal-organic frameworks (MOFs), i.e. UiO-66-X. The -X functional groups dangling on the MOF linkers could be regarded as location-specific remote microenvironment to regulate electronic properties of the single Cu atoms. Remarkably, they exhibit significant differences in the catalysis toward the hydroboration of alkynes. The activity follows the order of Cu1/UiO-66-NO2 ˃ Cu1/UiO-66 ˃ Cu1/UiO-66-NH2 under identical reaction conditions, where Cu1/UiO-66-NO2 showcases the phenylacetylene conversion of 92%, ~3.5 times higher efficiency than that of Cu1/UiO-66-NH2. Experimental and calculation results jointly support that the Cu electronic structure is modulated by the location-specific microenvironment, thereby regulating the product desorption and promoting the catalysis.

Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation

Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential to modify the size of its one-dimensional pore channels and the hydrophobicity of pore walls using various linker ligands during synthesis. Thermal activation of these materials yields accessible open metal sites (i.e., under-coordinated metal centers) at the pore walls, thus acting as strong primary binding sites for guest molecules, including water. We study the effect of the pore size and linker hydrophobicity within a series of Ni2+-based isoreticular frameworks (i.e., Ni2L, L = dhtp, dhip, dondc, bpp, bpm, tpp), analyzing their water sorption behavior and the water interactions in the confined pore space. For this purpose, we apply water vapor sorption analysis and Fourier transform infrared spectroscopy. In addition, defect degrees of all compounds are determined by thermogravimetric analysis and solution 1H nuclear magnetic resonance spectroscopy. We find that larger defect degrees affect the preferential sorption sites in Ni2dhtp, while no such indication is found for the other materials in our study. Instead, strong evidence is found for the formation of water bridges/chains between coordinating water molecules, as previously observed for hydrophobic porous carbons and mesoporous silica. This suggests similar sorption energies for additional water molecules in materials with larger pore sizes after saturation of the primary binding sites, resulting in more bulk-like water arrangements. Consequently, the sorption mechanism is driven by classical pore condensation through H-bonding anchor sites instead of sorption at discrete sites.

Loading Dyes into Chiral Cd/Zn‐Metal–Organic Frameworks for Efficient Full‐Color Circularly Polarized Luminescence

AbstractHost‐guest chemistry of chiral metal‐organic frameworks (MOFs) has endowed them with circularly polarized luminescence (CPL), it is still limited for MOFs to systematically tune full‐color CPL emissions and sizes. This work directionally assembles the chiral ligands, metal sites and organic dyes to prepare a series of crystalline enantiomeric D/L‐Cd/Zn‐n MOFs (n=1~5, representing the adding amount of dyes), where D/L‐Cd/Zn with the formula of Cd2(D/L–Cam)2(TPyPE) and Zn2(D/L–Cam)2(TPyPE) (D/L‐Cam=D/L‐camphoric acid, TPyPE=4,4’,4’’,4’’’‐(1,2‐henediidenetetra‐4,1‐phenylene)tetrakis[pyridine]) were used as the chiral platforms. The framework‐dye‐enabled emission and through‐space chirality transfer facilitate D/L‐Cd/Zn‐n bright full‐color CPL activity. The ideal yellow CPL of D‐Cd‐5 and D‐Zn‐4, with |glum| as 4.9 × 10−3 and 1.3×10−3 and relatively high photoluminescence quantum yield of 40.79 % and 45.40 %, are further assembled into a white CPL light‐emitting diode. The crystal sizes of D/L‐Cd/Zn‐n were found to be strongly correlated to the types and additional amounts of organic dyes, that the positive organic dyes allow for the preparation of > 7 mm bulks and negative dyes account for sub‐20 μm particles. This work opens a new avenue to fabricate full‐color emissive CPL composites and provides a potentially universal method for controlling the size of optical platforms.

Surface Coordination Chemistry of Graphitic Carbon Nitride from Ag Molecular Probes.

Graphitic carbon nitride (g-C3N4) has gained significant attention for its catalytic properties,especiallyin the development of Single Atom Catalysts (SACs).However,the surface chemistry underlying the formation of these isolated metal sites remains poorly understood.In thisstudyweemploy Surface OrganoMetallic Chemistry (SOMC) together with advanced microscopic and spectroscopic techniquesfor an in-depth analysis of functionalizedg-C3N4materials, where tailored organosilver probe molecules are used to monitor surface processes and characterize resulting surface species. Amulti-technique approach-including high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM), X-ray absorption spectroscopy (XAS), and multinuclear solid-state Nuclear Magnetic Resonance spectroscopy (ssNMR),coupled with density functional theory (DFT) calculations- identifies three primary surface speciesin Ag-functionalized g-C3N4:bis-NHC-Ag+, dispersed Ag+sites, andphysisorbed molecular precursor.These findings highlight a dynamic grafting process and provide insights into the surface coordination chemistryof functionalizedg-C3N4materials.

Metalloid Phosphorus Induces Tunable Defect Engineering in High Entropy Oxide Toward Advanced Lithium‐Ion Batteries

AbstractThe inferior electrical conductivity and sluggish lithium storage kinetics of conventional high‐entropy oxide (HEO) are critical issues hindering their commercialization. The high electronegativity of metalloids can ameliorate this predicament by altering the electronic configuration of HEO compared to metals. Herein, metalloid phosphorus doping in spinel‐type HEO (PxA1‐x)B2O4 (A/B = Cr, Mn, Fe, Co, Ni) (P‐HEO) is achieved through a facile sol–gel process. The metalloid phosphorus doping facilitates the transfer of electrons from transition metal sites to phosphorus‐doped sites, resulting in the formation of electron‐rich and electron‐deficient local regions on the HEO surface and is conducive to an increase in the total number of active lithium sites in the electrochemical reaction process. Density functional theory calculation reveals Li adsorption energy on the synthesized P‐HEO is only −1.102 eV, demonstrating that the phosphorus doping enables a strong electronic coupling between lithium ions and P‐HEO. Furthermore, metalloid phosphorus doping also leads to oxygen vacancies formation and lattice distortion, which significantly enhances charge transfer efficiency and diffusion kinetics and results in the enhanced lithium storage performance with impressive rate capability and long‐term stability. These findings provide valuable insights for the design of lattice‐engineered HEO as versatile electrodes for future energy storage applications.

Modulating the Local Coordination Environment of M‐Nx Single‐Atom Site for Enhanced Electrocatalytic Oxygen Reduction

AbstractEfficient, durable, and economical oxygen reduction catalysts are key for practical applications such as fuel cells and metal–air batteries. Single atom catalysts (SACs) have attracted sustained and widespread attention owing to their unique electronic properties and exceptional atomic utilization, positioning them as promising electrocatalysts in energy conversion and storage. However, the symmetric charge distribution of the metal site in the symmetric M‐N4 configuration of SACs is not conducive to electron transfer and transport in electrocatalytic reactions, resulting in a low adsorption energy for oxygen reduction reaction (ORR) related species (*OH, *O, and *OOH), which severely limits the intrinsic activity of the electrocatalysts. To overcome this limitation and improve the activity and durability, heteroatom doping can effectively modulate the local coordination environment (LCE) of the metal atom, including the coordinating atoms, coordination shells and coordination number. These modifications have significantly improved the performance of carbon supported SACs with M‐N4 configuration in the ORR. Based on this, a thorough summary of the major progress made in recent years in adjusting the LCE of SACs through doping with heteroatoms is provided and a perspective on the future development is offered here.