A nitrogen-rich covalent organic framework material (SNW-1) was prepared via oil bath reflux method. Metal center Fe was introduced by a post-doping strategy, and the Fe-N-SNW-1 catalyst was synthesized through calcination. The electrocatalytic performance of this catalyst for the oxygen reduction reaction (ORR) was investigated. The crystal struc-ture and elemental chemical states of the Fe-N-SNW-1 catalyst were comprehensively characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and other techniques. Electrochemical tests including cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to explore its ORR electrocatalytic activity. The results show that the Fe-N-SNW-1 catalyst exhibits a microspherical morphology, high graphitic nitrogen content, and excellent ORR electrocatalytic performance. Analysis of key electrochemical parameters indicates that the Fe-N-SNW-1 catalyst has an onset potential of 0.975 V vs. RHE and a half-wave potential of 0.841 V vs. RHE.
References
[1]
Ferrandon, M., Kropf, A.J., Myers, D.J., Artyushkova, K., Kramm, U., Bogdanoff, P., et al. (2012) Multitechnique Characterization of a Polyani-line-Iron-Carbon Oxygen Reduction Catalyst. The Journal of Physical Chemistry C, 116, 16001-16013.
https://doi.org/10.1021/jp302396g
[2]
Guo, Y., Wang, Z., Wang, Y., Ma, L., Zhang, N. and Jiang, R. (2022) Efficient Oxygen Reduction Electrocatalyst Derived from Facile Fe,N-Surface Treatment of Carbon Black. Journal of Colloid and Interface Science, 605, 101-109.
https://doi.org/10.1016/j.jcis.2021.07.071
[3]
Hao, Y., Wang, L. and Huang, L. (2023) Lanthanide-Doped MoS2 with Enhanced Oxygen Reduction Activity and Biperiodic Chemical Trends. Nature Communications, 14, Article No. 3256. https://doi.org/10.1038/s41467-023-39100-5
[4]
Wang, Q., Chen, Z., Wu, N., Wang, B., He, W., Lei, Y., et al. (2017) N-Doped 3D Carbon Aerogel with Trace Fe as an Efficient Catalyst for the Oxygen Reduction Reaction. ChemElectroChem, 4, 514-520. https://doi.org/10.1002/celc.201600799
[5]
Bhoyate, S.D., Kim, J., de Souza, F.M., Lin, J., Lee, E., Kumar, A., et al. (2023) Science and Engineering for Non-Noble-Metal-Based Electrocatalysts to Boost Their ORR Performance: A Critical Review. Coordination Chemistry Reviews, 474, Article ID: 214854. https://doi.org/10.1016/j.ccr.2022.214854
[6]
Musgrave, C.B., Su, J., Xiong, P., Song, Y., Huang, L., Liu, Y., et al. (2025) Molecular Strain Accelerates Electron Transfer for Enhanced Oxygen Reduction. Journal of the American Chemical Society, 147, 3786-3795. https://doi.org/10.1021/jacs.4c16637
[7]
Yamazaki, S., Asahi, M., Taguchi, N. and Ioroi, T. (2019) Electrochemical Analysis of the Porphyrazine-Induced Enhancement of ORR Activity of Pt Catalysts for the Development of Porphyrazine-Adsorbed Pt Catalysts. Journal of Electroanalytical Chemistry, 848, Article ID: 113321. https://doi.org/10.1016/j.jelechem.2019.113321
[8]
Qian, Y., Khan, I.A. and Zhao, D. (2017) Electrocatalysts Derived from Metal-Organic Frameworks for Oxygen Reduction and Evolution Reactions in Aqueous Media. Small, 13, Article ID: 1701143. https://doi.org/10.1002/smll.201701143
[9]
Zhang, Y. and Guo, Z. (2023) Transition Metal Compounds: From Properties, Applications to Wettability Regulation. Advances in Colloid and Interface Science, 321, Article ID: 103027. https://doi.org/10.1016/j.cis.2023.103027
[10]
Wang, Y., Li, J. and Wei, Z. (2018) Transition-Metal-Oxide-Based Catalysts for the Oxygen Reduction Reaction. Journal of Materials Chemistry A, 6, 8194-8209.
https://doi.org/10.1039/c8ta01321g
[11]
Araújo, H., Sljukc, B., Gago, S. and Santos, D.M.F. (2024) The Current State of Transition Metal-Based Electrocatalysts (Oxides, Alloys, POMs, and MOFs) for Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution Reactions. Frontiers in Energy Research, 12, Article ID: 1373522. https://doi.org/10.3389/fenrg.2024.1373522
[12]
Shen, Y., Li, B., Zhang, Z., Liu, J., Ren, H., Zhou, Y., et al. (2025) Selective Adsorption-Catalytic Action of Spinel Sulfur Reduction Catalyst Based on Geometric Structure Regulation on Lithium Polysulfide. Electrochimica Acta, 541, Article ID: 147345.
https://doi.org/10.1016/j.electacta.2025.147345
[13]
Xiao, L., Qi, L., Sun, J., Husile, A., Zhang, S., Wang, Z., et al. (2024) Structural Regulation of Covalent Organic Frameworks for Advanced Electrocatalysis. Nano Energy, 120, Article ID: 109155. https://doi.org/10.1016/j.nanoen.2023.109155
[14]
Samarasinghe, S.A.S.C., Chuah, C.Y., Li, W., Sethunga, G.S.M.D.P., Wang, R. and Bae, T. (2019) Incorporation of Coiii Acetylacetonate and SNW-1 Nanoparticles to Tailor O2/N2 Separation Performance of Mixed-Matrix Membrane. Separation and Purification Technology, 223, 133-141. https://doi.org/10.1016/j.seppur.2019.04.075
[15]
Vatanpour, V., Tuncay, G., Teber, O.O., Paziresh, S., Tavajohi, N. and Koyuncu, I. (2024) Introducing the SNW-1 Covalent Organic Framework to the Polyamide Layer of the TFC-RO Membrane with Enhanced Permeability and Desalination Performance. ACS Applied Materials & Interfaces, 16, 65194-65210.
https://doi.org/10.1021/acsami.4c14923
[16]
Qu, X., Li, Y., Li, G., Ji, R., Yin, S., Cheng, X., et al. (2022) Boosting the ORR Performance of Fe-N/C Catalyst via Increasing the Density and Modifying the Electronic Structure of Fe-Nx Active Sites. Electrochimica Acta, 403, Article ID: 139604.
https://doi.org/10.1016/j.electacta.2021.139604
[17]
Wei, X., Cao, S., Cheng, S., Lu, C., Chen, X., Lu, X., et al. (2025) Heterometallic Doping Regulation in Two-Dimensional Metal-organic Frameworks for Enhanced Electrocatalytic Oxygen Reduction Reaction: A Computational Study. Applied Surface Science, 713, Article ID: 164331. https://doi.org/10.1016/j.apsusc.2025.164331
[18]
Cheng, J., Lyu, C., Chen, H., Geng, D. and Zheng, J. (2024) Strong Lewis Acid-Base Interfacial Regulation Mechanism to Reveal Oxygen Reduction Activity Origin of N,S-Codoped Carbon with PtNi Particles. Chemical Engineering Journal, 482, Article ID: 149070. https://doi.org/10.1016/j.cej.2024.149070
[19]
Li, X., Wang, D., Xu, H., Zha, S., Wang, W., Mitsuzaki, N., et al. (2025) Graphitic N-C-P Configuration of Phosphorus and Nitrogen Co-Doped Carbon for Boosting the Oxygen Electroreduction. Applied Surface Science, 683, Article ID: 161814.
https://doi.org/10.1016/j.apsusc.2024.161814
[20]
Yuan, H., Liu, P., Ren, J., Jiang, Z., Wang, X. and Zhao, H. (2024) Carbon Dot Hybrid Porous Carbon Nanofibers as Efficient Electrocatalysts for the Oxygen Reduction Reaction. Materials Chemistry Frontiers, 8, 1643-1650.
https://doi.org/10.1039/d3qm01064c
[21]
Malik, H. and Nadeem, M.A. (2025) Unlocking the Two Electron ORR: Synergistic Roles of MOFs and COFs in Mechanistic Insights and Performance Optimization. Coordination Chemistry Reviews, 544, Article ID: 216977.
https://doi.org/10.1016/j.ccr.2025.216977
[22]
Li, C., Wang, Z., Jin, Y., Li, Z., Jeon, J., Zhao, S., et al. (2025) Tunable Catalytic Vertex Wall Chemistry in Metal-Free Covalent Organic Frameworks for Enhanced Oxygen Reduction. Angewandte Chemie International Edition, 64, e202500336.
https://doi.org/10.1002/anie.202500336
[23]
Du, L., Li, X., Lu, X. and Guo, Y. (2024) The Synthesis Strategies of Covalent Organic Frameworks and Advances in Their Application for Adsorption of Heavy Metal and Radionuclide. Science of the Total Environment, 939, Article ID: 173478.
https://doi.org/10.1016/j.scitotenv.2024.173478
[24]
Ma, Y., Kuang, X., Deng, X., Zi, B., Zeng, J., Zhang, J., et al. (2022) The Recent Research Progress and Application of Nanoparticles and Ions Supporting by Covalent Organic Frameworks. Microporous and Mesoporous Materials, 335, Article ID: 111701. https://doi.org/10.1016/j.micromeso.2022.111701
[25]
Lee, E., Shin, S., Lee, H. and Ham, H.C. (2025) Role of Pz Band in Hybrid Carbon-Bimetallic Subnanocluster PtM (M = 3d, 4d, 5d Block Metals) Catalysts to Boost Electrochemical Oxygen Reduction Reaction. Applied Surface Science Advances, 28, Article ID: 100792. https://doi.org/10.1016/j.apsadv.2025.100792
[26]
Li, M.-Y., Liu, J., Gao, R., Lin, D.-Y., Wang, F. and Zhang, J. (2021) Design and Synthesis of Zeolitic Tetrazolate-Imidazolate Frameworks. Materials Today Advances, 10, Article ID: 100145. https://doi.org/10.1016/j.mtadv.2021.100145
[27]
Kim, D., Nguyen, A.N. and Yoo, H. (2025) Iron Doping of Coordination Polymer Nanocubes and Post-Thermolysis for Efficient Oxygen Reduction Reaction Single-Atom Catalysis. Journal of Power Sources, 641, Article ID: 236812.
https://doi.org/10.1016/j.jpowsour.2025.236812
[28]
Gan, R., Wang, Y., Zhang, X., Song, Y., Shi, J. and Ma, C. (2023) Edge Atomic Fe Sites Decorated Porous Graphitic Carbon as an Efficient Bifunctional Oxygen Catalyst for Zinc-Air Batteries. Journal of Energy Chemistry, 83, 602-611.
https://doi.org/10.1016/j.jechem.2023.03.056
[29]
Fang, L., Li, Y., Zhang, M., Qiu, H., Geng, H., Tao, Y., et al. (2024) Anchored Fe3O4/Fe Nanoparticles on Hollow PPy Nanotube@Fe-Modified ZIF-8 Derivative for Enhanced ORR Activity in Zinc-Air Batteries. Diamond and Related Materials, 149, Article ID: 111621. https://doi.org/10.1016/j.diamond.2024.111621
[30]
Qi, J., Wang, W., Li, Y., Sun, Y., Wu, Z., Bao, K., et al. (2022) On-Chip Investigation of Electrocatalytic Oxygen Reduction Reaction of 2D Materials. Small, 18, Article ID: 2204010. https://doi.org/10.1002/smll.202204010
[31]
Geng, K., He, T., Liu, R., Dalapati, S., Tan, K.T., Li, Z., et al. (2020) Covalent Organic Frameworks: Design, Synthesis, and Functions. Chemical Reviews, 120, 8814-8933.
https://doi.org/10.1021/acs.chemrev.9b00550
[32]
Williams, J.H., Gbadomosi, M., Greytak, A.B. and Myrick, M.L. (2023) Measuring the Surface Area of Carbon Black Using BET Isotherms: An Experiment in Physical Chemistry. Journal of Chemical Education, 100, 4838-4844.
https://doi.org/10.1021/acs.jchemed.3c00764
