Oxygen Reduction Reaction Catalytic Performance Research Articles

NC Loaded PtM Alloy from M-NC with Ultralow Pt Loading for Oxygen Reduction Reaction

Developing low Pt or non-precious metal catalysts for oxygen reduction reaction (ORR) has becoming necessary in recent years. Herein, PtM alloy anchored on nitrogen-doped carbon (PtM/NC, M=Fe, Co) catalyst with ultralow Pt loading (∼1 wt%) is prepared from the simple two-process pyrolysis, namely from C to M-NC then to PtM/NC. The as-prepared PtM/NC (M=Fe, Co) shows an excellent ORR catalytic performance with the peak potential and half-wave potential of 0.901 and 0.870 V for PtFe/NC, 0.868 and 0.845 V for Pt3Co/NC. The ORR on PtM/NC (M=Fe, Co) is a mainly direct 4-electron reaction pathway (3.75–3.90) in alkaline solution. Moreover, they possess good methanol tolerance and stability. Synergistic effect of Pt and M together with N species result in the excellent ORR catalytic activity of PtM/NC (M=Fe, Co). The negative shift of Pt binding energy caused by both lattice contraction and electron orbital coupling from M is beneficial for reducing the d-band center of Pt, weakening the oxygen binding energy and enhancing the ORR intrinsic activity of Pt. The strong interactions between NC and PtM alloy are beneficial for anchoring PtM nanoparticles, promoting the stability of catalyst. This work provides a new strategy for preparing ultralow Pt loading catalysts.

Dealloyed Pt74Ni26 and Pt26Ni74 Electrodeposited Thin Film Electrocatalysts for Oxygen Reduction

Abstract Electrodeposition and microstructure of thin films close to Pt75Ni25 and Pt25Ni75 stoichiometry are described and their catalytic oxygen reduction reaction performance, dealloying, and strain evolution detailed. Multiple techniques are used to characterize the morphology, crystalline structure, and chemical homogeneity of as-deposited and dealloyed films. A fine-scale percolating network of lower-density regions is evident in the as-deposited Pt74Ni26 films while the as-deposited Pt26Ni74 films are more homogenous and compact. Electrodeposition is accompanied by development of significant in-plane tensile stress that increases at more negative applied growth potentials to reach 1.28 GPa for as-deposited Pt26Ni74. Dealloying of the near-surface regions of Pt74Ni26 is accompanied by limited expansion or opening of the low-density regions while massive dealloying of the highly stressed Pt26Ni74 results in shrinkage, extensive cracking, and formation of a bi-continuous nanoporous structure with an average pore diameter close to 5 nm. Relative to electrodeposited Pt, the alloy films exhibit enhanced area-specific oxygen reduction reaction activity (at 0.95 V vs. RHE, iR-corrected) that amounts to a factor of 3.4 for dealloyed Pt74Ni26 and 5.1 for dealloyed Pt26Ni74 while the Pt-based mass activity increased by a factor of 5.1 and 12.3, for the respective films.

An improvement on the electrocatalytic performance of ZIF-67 by in situ self-growing CNTs on surface

Efficient and robust oxygen reduction reaction (ORR) catalysts are essential for the development of high-performance anion-exchange membrane fuel cells (AEMFC). To enhance the electrochemical performance of metal–organic frameworks of cobalt-based zeolite imidazolium skeleton (ZIF-67), this study reported a novel ZIF-67-4@CNT by in situ growing carbon nanotubes (CNTs) on the surface of ZIF-67 via a mild two-step pyrolysis/oxidation treatment. The electrochemical results showed that the as-prepared ZIF-67-4@CNT after CTAB modification exhibited excellent catalytic activity with good stability, with Eonset, E1/2, and Ilimit, respectively were 0.98 V (versus RHE), 0.87 V (versus RHE) and 6.04 mA cm−2@1600 rpm, and a current retention rate of about 94.21% after polarized at 0.80 V for 10 000 s, which were all superior to that of the commercial 20 wt% Pt/C. The excellent ORR catalytic performance was mainly attributed to the large amount of the in situ growing CNTs on the surface, encapsulated with a wide range of valence states of metallic cobalt.

Density functional theory study on the mechanism of oxygen reduction reaction on nitrogen-doped graphene with adjacent Mn and Ni sites

The catalysts for oxygen reduction reaction (ORR) are of great significance to the development of electrochemical energy systems. In this paper, the ORR catalytic performance of Mn–Ni dual-metal doped N-coordinated graphene is studied by density functional theory (DFT). The results show that the catalysts with dual-metal active sites are more stable than that with single metal site, and all catalysts show certain catalytic activity. The reaction pathway analyses of catalysts with two different adsorption configurations of O2 show that when O2 is adsorbed on two metal sites, OOH will automatically split into OH and O. When O2 is adsorbed on Mn site alone, the other site does not participate in the adsorption of oxygen-containing intermediates. The thermodynamic calculation results show that the catalytic performance is mainly influenced by the adsorption strength of O, which is controlled by the number of active sites involved in the adsorption, bond length and the number of transferred electrons at the active sites. The G-MnNiN6-3 shows the best catalytic performance with an overpotential of 0.453 V and a reaction energy barrier of 0.19 eV. The results of this study highlight the potential application of Mn–Ni dual-metal doped N-coordinated graphene as a highly efficient non-precious catalyst.

Heteroatom-Doped Carbon-Based Catalysts Synthesized through a “Cook-Off” Process for Oxygen Reduction Reaction

The development of efficient and low-cost non-metallic catalysts is of great significance for the oxygen reduction reaction (ORR) in fuel cells. Heteroatom-doped carbon-based catalysts are one of the popular candidates, although their preparation method is still under exploration. In this work, single (CS)-, double (NCS)-, and triple (NBCS)-heteroatom-doped carbon-based catalysts were successfully prepared by a “cook-off” process. The morphology, elemental composition, and bonding structure of the catalysts were investigated by SEM, TEM, Raman spectra, BET, and XPS. ORR catalytic performance measurements suggested an activity trend of CS < NCS < NBCS, and NBCS demonstrated better methanol resistance and slightly higher stability than the commercial Pt/C catalyst, as evaluated with both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) systems. The mechanism for the promoted performance was also proposed based on the conductivity of the catalysts. In this paper, the heteroatoms N, B, and S were co-doped into activated carbon using a simple, fast, and efficient preparation method with high electrical conductivity and also increased active sites, showing high electrocatalytic activity and good stability. This work provides a new approach to preparing highly active non-Pt catalysts for oxygen reduction reactions.

Functionalized nitrogen doping induced manganese oxyhydroxide rooted in manganese sesquioxide rod for robust oxygen reduction electrocatalysis

The rational synthesis of hybrid catalysts with diverse electrocatalytically active components for robust oxygen reduction reaction (ORR) is highly desirable for the development of sustainable metal-air batteries. By using melamine as nitrogen and hydrogen precursors, herein, melamine pyrolysis-induced functionalized nitrogen doping was adopted for the construction of nitrogen doped manganese oxides (N-MnOx Rs), which consists of manganese oxyhydroxide (MnOOH) rooted in manganese sesquioxide (Mn2O3) rod, as a robust ORR electrocatalyst. Systematic studies have found that a suitable mass ratio of melamine to β-MnO2 rods is necessary for the formation of electrocatalytically MnOOH and Mn2O3. The representative N-MnOx Rs exhibits the nano structure consisting of interconnected nonorods, nanowires, and nanoparticles, which not only increases the exposure of more active sites but also enhances microstructure stability. Moreover, the nitrogen doping creates high content of oxygen vacancies, which accelerates electron transmission/transfer of N-MnOx Rs. As a result, the optimal N-MnOx Rs exhibits impressive ORR catalytic performance in a homemade ZAB. The N-MnOx Rs driven ZAB (176.6 mW cm-2; 811 mAh g-1) delivers a high peak power density and large discharging capacitance comparable to Pt/C driven one (178.1 mW cm-2; 800 mAh g-1), displaying a promising application potential. This work provides a functionalized nitrogen doping strategy for rational construction of robust hybrid electrocatalysts for energy conversion.

Ferromagnetic L12‐Pt3Co Nanowires with Spin‐Polarized Orbitals for Fast and Selective Oxygen Reduction Electrocatalysis

AbstractMagnetic alloys are key to develop efficient catalysts for oxygen reduction reaction (ORR) in fuel cells. During the last decade, it has been shown that spin manipulation of magnetic materials can improve the kinetics of triplet state 3O2 electrocatalysis, promoting the unification between the physics of strongly correlated materials and heterogeneous catalysis. In this study, structurally ordered Pt3Co nanowires (NWs) are synthesized, and their ORR catalytic performances are studied in detail. These intermetallic ordered L12‐Pt3Co NWs exhibit stronger ferromagnetism, superior ORR catalytic activity, and higher tolerance to carbon monoxide than related disordered A1‐Pt3Co NWs, and commercial Pt/C catalyst. These characteristics make them one of (if not) the best catalyst reported nowadays. Density functional theory calculations prove that the L12‐Pt3Co(111) surface displays a lower activation barrier at the ORR rate‐limiting step and better selectivity H2O2/H2O (i.e., lower production of H2O2) compared with disordered A1‐Pt3Co(111). ORR reactivity increases with the level of Co order in the slab. Moreover, L12‐Pt3Co(111) displays more favorable thermodynamics, decreasing the adsorption enthalpies of 3O2, and lower ORR rate‐limiting step, due to ferromagnetic quantum spin exchange interactions (QSEI), compared with Pt(111).

Concave Structural Carbon Co-Doped with Iron Atom Pairs and Nitrogen as Ultra-High Performance Catalyst Toward Oxygen Reduction.

It is crucial to rationally design and synthesize atomic-scale transition metal-doped carbon catalysts with high electrocatalytic activity to achieve a high-efficient oxygen reduction reaction (ORR). Herein, an electrocatalyst comprised of Fe-Fe dual atom pairs and N-doped concave carbon are reported (N-CC@Fe DA) that achieves ultrahigh electrocatalytic ORR activity. The catalyst is prepared by a gaseous doping approach, with zeolitic imidazolate framework-8 (ZIF-8) as the carbon framework precursor and cyclopentadienyliron dicarbonyl dimer as the Fe-Fe atom pair precursor. The catalyst exhibits high cathodic ORR catalytic performance in an alkaline Zn/air battery and proton exchange membrane fuel cell (PEMFC), yielding peak power densities of 241 mW cm-2 and 724mWcm-2, respectively, compared to 127 mW cm-2 and 1.20Wcm-2 with conventional Pt/C catalysts as cathodes. The presence of Fe atom pairs coordinate with N atoms is revealed by X-ray photoelectron spectroscopy(XPS) and X-ray absorption spectroscopy (XAS) analysis, and Density Functional Theory (DFT) calculation results show that the Fe-Fe pair structure is beneficial for adsorbing oxygen molecules, activating the O─O bond, and desorbing OH* intermediates formed during oxygen reduction, resulting in a more efficient oxygen reaction. The findings may provide a new pathway for preparing ultra-high-performance doped carbon catalysts with Fe-Fe atom pair structures.

Engineering Mn–Nx sites on porous carbon via molecular assembly strategy for long-life zinc-air batteries

Nitrogen-coordinated manganese atoms on carbon materials denoted as MnNC, serve as the highly active non-precious metal electrocatalysts for oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Nonetheless, a significant challenge arises from the tendency of Mn atoms to aggregate during heat treatment, thereby compromising ORR performance in ZABs. In this work, the molecular assembly strategy based on the hydrogen bond interaction was employed to fabricate the MnNC electrocatalyst. This approach promotes the dispersion of Mn atoms, creating abundant Mn–Nx active sites. Furthermore, the resulting three-dimensional porous nanostructure, formed by molecular assembly, significantly enhances accessibility to the Mn–Nx active sites. The porous nanostructure not only shortens the diffusion path of reactants and charges but also improves mass transfer. The MnNC exhibits impressive ORR catalytic performance with a half-wave potential of 0.90 V (vs. RHE). The liquid-type ZAB based on MnNC displays a high specific capacity of 816.6 mAh/g and an extended charge–discharge cycle life of 1000 h. Quasi-solid-state ZAB based on MnNC can operate stably for 24 h. This work presents an effective strategy to synthesize transition metal-nitrogen-carbon (MNC) electrocatalysts tailored for long-life zinc-air battery.

Simultaneous introduction of iodine and Fe-Nx into carbon nanospheres for enhanced catalytic activity towards oxygen reduction using a solution plasma process

The oxygen reduction reaction (ORR) plays a critical role at the cathode of fuel cells and metal–air batteries. In this study, we report the one-pot synthesis of iodine- and Fe-Nx impregnated carbon nanospheres (FeNI-CNS) using a solution plasma process and their effect on electrocatalytic activity. FeNI-CNS exhibits a fast four-electron transfer reaction with a high current density and superior durability in both alkaline and acidic media. The excellent catalytic performance is attributed to the synergetic effect between the iodine and Fe-Nx sites, which provide a higher reaction rate and faster ORR, respectively. We believe that these findings represent a new approach for enhancing ORR catalytic performance and catalyst synthesis.

Precise Modulation of Carbon Activity Sites in Metal-Free Covalent Organic Frameworks for Enhanced Oxygen Reduction Electrocatalysis.

Metal-free carbon-based materials have gained recognition as potential electrocatalysts for the oxygen reduction reaction (ORR) in new environmentally-friendly electrochemical energy conversion technologies. The presence of effective active centers is crucial for achieving productive ORR. In this study, we present the synthesis of two metal-free dibenzo[a,c]phenazine-based covalent organic frameworks (DBP-COFs), specifically JUC-650 and JUC-651, which serve as ORR electrocatalysts. Among them, JUC-650 demonstrates exceptional catalytic performance for ORR in alkaline electrolytes, exhibiting an onset potential of 0.90V versus RHE and a half-wave potential of 0.72V versus RHE. Consequently, JUC-650 stands out as one of the most outstanding metal-free COF-based ORR electrocatalysts report to date. Experimental investigations and density functional theory calculations confirm that modulation of the frameworks' electronic configuration allows for the reduction of adsorption energy at the Schiff-base carbon active sites, leading to more efficient ORR processes. Moreover, the DBP-COFs can be assembled as excellent air cathode catalysts for zinc-air batteries (ZAB), rivaling the performance of commercial Pt/C. This study provides valuable insights for the development of efficient metal-free organoelectrocatalysts through precise regulation of active site strategies.

Biaxially‐Strained Phthalocyanine at Polyoxometalate@Carbon Nanotube Heterostructure Boosts Oxygen Reduction Catalysis

AbstractIron phthalocyanine (FePc) with unique FeN4 site has attracted increasing interests as a promising non‐precious catalyst. However, the plane symmetric structure endows FePc with undesired catalytic performance toward the oxygen reduction reaction (ORR). Here, we report a novel one‐dimensional heterostructured ORR catalyst by coupling FePc at polyoxometalate‐encapsulated carbon nanotubes (FePc‐{PW12}@NTs) using host‐guest chemistry. The encapsulation of polyoxometalates can induce a local tensile strain of single‐walled NTs to strengthen the interactions with FePc. Both the strain and curvature effects of {PW12}@NT scaffold tune the geometric structure and electronic localization of FeN4 centers to enhance the ORR catalytic performance. As expected, such a heterostructured FePc‐{PW12}@NT electrocatalyst exhibits prominent durability, methanol tolerance, and ORR activity with a high half‐wave potential of 0.90 V and a low Tafel slope of 30.9 mV dec−1 in alkaline medium. Besides, the assembled zinc‐air battery demonstrates an ultrahigh power density of 280 mW cm−2, excellent charge/discharge ability and long‐term stability over 500 h, outperforming that of the commercial Pt/C+IrO2 cathode. This study offers a new strategy to design novel heterostructured catalysts and opens a new avenue to regulate the electrocatalytic performance of phthalocyanine molecules.

Biaxially-Strained Phthalocyanine at Polyoxometalate@Carbon Nanotube Heterostructure Boosts Oxygen Reduction Catalysis.

Iron phthalocyanine (FePc) with unique FeN4 site has attracted increasing interests as a promising non-precious catalyst. However, the plane symmetric structure endows FePc with undesired catalytic performance toward the oxygen reduction reaction (ORR). Here, we report a novel one-dimensional heterostructured ORR catalyst by coupling FePc at polyoxometalate-encapsulated carbon nanotubes (FePc-{PW12}@NTs) using host-guest chemistry. The encapsulation of polyoxometalates can induce a local tensile strain of single-walled NTs to strengthen the interactions with FePc. Both the strain and curvature effects of {PW12}@NT scaffold tune the geometric structure and electronic localization of FeN4 centers to enhance the ORR catalytic performance. As expected, such a heterostructured FePc-{PW12}@NT electrocatalyst exhibits prominent durability, methanol tolerance, and ORR activity with a high half-wave potential of 0.90 V and a low Tafel slope of 30.9 mV dec-1 in alkaline medium. Besides, the assembled zinc-air battery demonstrates an ultrahigh power density of 280 mW cm-2, excellent charge/discharge ability and long-term stability over 500 h, outperforming that of the commercial Pt/C+IrO2 cathode. This study offers a new strategy to design novel heterostructured catalysts and opens a new avenue to regulate the electrocatalytic performance of phthalocyanine molecules.

Mesoporous and dual-shelled hollow CeO2@CoNC nanospheres as efficient and stable oxygen reduction reaction electrocatalysts

The electrocatalytic oxygen reduction reaction (ORR) is the key bottleneck of fuel cells and rechargeable metal-air batteries, and recently, metalnitrogen complex carbon (MNC) demonstrates great potential in these fields. However, the complex and easily degraded MNC structure often results in inferior activity and poor durability in electrolysis. Herein, we fabricate a catalyst of h-CeO2@CoNC through the extended Stöber method and subsequent pyrolysis, involving the hollow CeO2 as the core and CoNC as the shell. The h-CeO2@CoNC catalyst exhibits notable ORR catalytic performances in 0.1 M KOH with a half-wave potential of 0.82 V and excellent durability, attributed to the synergistic interaction between CeO2 and CoNC matrix. Specifically, the inner layer of CeO2 is principally responsible for enhancing the chemical stability and the outer one of CoNC matrix is beneficial to boosting the ORR catalytic activity. This work provides an efficient preparation approach and further insight of rational design of the unique MNC catalysts for energy storage.

Triethylenediamine cobalt complex encapsulated in a metal–organic framework cage to prepare a cobalt single-atom catalyst with a high Co-N4 density for an efficient oxygen reduction reaction

Transition metal single atom catalysts (TM SACs) are the most promising oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, the low density of M-Nx active sites seriously hinders further improvement of the ORR electrocatalytic activity. Here, a strategy for encapsulating nitrogen-rich guest molecules (triethylenediamine cobalt complex, [Co(en)3]3+) was proposed to construct a high-performance cobalt single-atom catalyst (Co-encapsulated SAC/NC). With this strategy, the guest molecules are encapsulated into metal–organic framework (MOF) cages as an additional cobalt source to boost cobalt loading, while abundant nitrogen from guest molecules contributes to the formation of Co-N4 active sites. Remarkably, the resulting Co-encapsulated SAC/NC has a high cobalt loading amount of 4.03 wt%, and spherical aberration-corrected transmission electron microscopy (AC-TEM) has confirmed that most cobalt exists in a single-atom state. As a result, the Co-encapsulated SAC/NC exhibits excellent ORR catalytic performance with a half-wave potential of 0.88 V. Furthermore, Zn-air batteries employing Co-encapsulated SAC/NC as air cathode show high peak power density and excellent cycling stability. Density functional theory (DFT) calculations reveal that adjacent active sites have different rate-determining steps and lower reaction energy barriers than a single active site.

A potentially efficient ORR catalyst: Transition metal-doped 2D Haeckelite MoS2

Enhancing the efficiency of the proton exchange membrane fuel cell (PEMFC) relies significantly on the development of low-cost but highly efficient catalysts for oxygen reduction reaction (ORR). In the present work, a specially structured two-dimensional layered material called Haeckelite (HL) MoS2 is investigated as an electrocatalyst for ORR by using density functional theory (DFT). In order to further improve the ORR catalytic performance, transition metals (TMs = Mn, Ru, Rh and Os) are independently doped on the surface of HL-MoS2. The detailed calculation includes the TMs doping, O2 molecule adsorption, electronic structure analysis, and Gibbs free energy comparison. The final results demonstrate that all TM/HL-MoS2 systems exhibit metallic properties, especially Ru/HL-MoS2 has the best catalytic performance for ORR in view of its moderate adsorption energy of O2 molecule (≈ 0.57 eV) and the lowest overpotential (≈ 0.503 V). Therefore, the combination of defect structure and TMs doping in MoS2 can be regarded as an effective approach to achieve both enhancement of catalytic performance and reduction of consumption of precious metals in the oxygen reduction reaction.

Composite of iron phthalocyanine and reduced graphene oxide with low temperature hydrothermally grown Ti3C2Tx Mxene for ORR catalytic application

In this paper, Ti3C2Tx MXene was successfully prepared by a mild and environment-friendly low-temperature hydrothermal method. On this basis, the compsites FePc-M-rGO consisting of iron phthalocyanine (FePc), Ti3C2Tx MXene and reduced graphene oxide (rGO) were prepared through simple mixing and used as catalysts for oxygen reduction reaction (ORR). The materials were characterized by SEM, XRD and other methods. The effects of raw material ratio, hydrochloric acid concentration, reaction temperature and reaction time on the properties of Ti3C2Tx were studied in detail. Compared with hydrofluoric acid (HF) etching method, the Ti3C2Tx prepared by low-temperature hydrothermal method has larger layer spacing, more complete crystal structure, larger specific surface area and better conductivity. The influences of different ratios of each component of FePc-M-rGO on the ORR catalytic performances were investigated. Mainly attributed to the improvement of self stacking and uniform adhesion of FePc between Ti3C2Tx layer and graphene nanosheets, the optimized composite material has better ORR activity than commercially available Pt-C catalysts and has good application prospects. This work provides a new approach for the rapid and effective preparation of Ti3C2Tx Mxene, and provides new ideas for the design of non-noble metal catalysts for ORR.

Polyethylenimine-Ethylenediamine-Induced Pd Metallene toward Alkaline Oxygen Reduction.

Designing two-dimensional (2D) materials functionalized with organic molecules is an effective tactic to enhance catalytic performances for the oxygen reduction reaction (ORR). Herein, we synthesize Pd metallene with in situ modification of polyethylenimine-ethylenediamine (Pd@PEI-EDA metallene), in which PEI-EDA serves as both the structure-directing agent and modifier. Pd@PEI-EDA metallene has ample active sites and tuneable electronic structures due to ultrathin nanosheets with abundant wrinkles and interfacial structure. In contrast with commercial Pd/C and Pt/C, Pd@PEI-EDA metallene displays preferable catalytic ORR performance under alkaline conditions. This work offers an in situ interface engineering tactic for the preparation of 2D polymer-metal electrocatalysts to boost the ORR performance.

Multifunctional catalytic activity of Cu3N (001) surface: A first-principles study

Multifunctional catalysts that exhibit high catalytic performance for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) in a single material hold great promise for broad-spectrum applications, including overall water splitting, fuel cells, and metal–air batteries. In this first-principles study, Cu 3 N is computationally demonstrated as a multifunctional electrocatalyst for the HER, OER, and ORR owing to the unique coordination of N and Cu atoms on the (001) surface. Cu 3 N exhibits better HER catalytic activity than noble Pt-based catalysts. Furthermore, its OER and ORR catalytic activity is comparable to that of commercialized unifunctional catalysts, and its 4e – pathway selectivity is high during the ORR. The catalytic performance of the ORR is significantly improved by the introduction of vacancy defects. The integration of highly efficient HER, OER, and ORR catalytic performance in earth-abundant Cu 3 N not only opens an avenue for developing cost-efficient omnipotent catalysts but also facilitates advances in clean and renewable energy.

Se Atom Doping Enhances the Catalytic Activity of Co@NC for Oxygen Reduction Reaction

As the most promising nonprecious metal oxygen reduction reaction (ORR) catalyst, Co@NC catalysts have attracted much attention. Herein, to further improve the activity of Co@NC catalysts, Co and Se atoms are embedded in metal organic framework‐derived nitrogen‐doped porous carbon (NC) using a high‐temperature reduction strategy, and then Co–Se@NC catalysts are constructed. The ORR catalytic activity of the catalysts is evaluated by rotating disc electrodes, and the results show that the ORR catalytic activity of the Co–Se@NC catalysts is significantly enhanced compared to the Co@NC and Se@NC catalysts, demonstrating that the introduction of Se atoms into Co@NC catalysts can significantly improve the ORR catalytic activity. Spectral characterization and pore size analysis shows that the introduction of Se atoms has multiple effects, including providing new active sites, improving the pore structure of the catalyst, and promoting electron transfer and mass transport. This study shows that the Co–Se@NC catalysts has excellent catalytic performance for ORRs, reaching half‐wave potentials of 0.765 V in acidic electrolytes and 0.831 V in alkaline electrolytes, demonstrating that the introduction of Se atoms can effectively improve the ORR catalytic activity, thus providing a unique insight into the rational construction of ORR catalysts.