Fe-Facilitated Deep Reconstruction of Ni₃S₂ Toward Superior Oxygen Evolution

Abstract

The advancement of effective and stable non-precious metal-based catalysts for oxygen evolution reactions (OER) with a low-cost and simple technique is essential for the practical application of rechargeable zinc–air battery (ZAB). However, facilitating the deep reconstruction of electrocatalysts to form active species remains a significant challenge. Here, a simple two-step method composed of impregnation and carbonization process is proposed to synthesize N, S co-doped microcrystalline cellulose-derived carbon-supported nickel sulfide (Ni₃S₂) nanoparticles. The in situ Raman reveals that Fe substitution promotes the reconstruction of Ni₃S₂, accompanied by the cleavage of the Ni–S bond, leading to the deep reconstruction into (Ni,Fe)OOH (DR-(Ni,Fe)OOH) during the OER. Moreover, density functional theory calculations reveal that Fe substitution induces a downshift in the energy band structure, which lowers the energy barriers and thereby improves the kinetics of the OER. The generated DR-(Ni,Fe)OOH delivers a relatively low overpotential of 260 mV and superior durability for 50 h under OER condition. The ZAB incorporating DR-(Ni,Fe)OOH + Pt/C as the air cathode demonstrates superior efficiency and durability, achieving a peak power density of 188.3 mW cm⁻², a specific capacity of 811.1 mAh g⁻¹, and long-term stability exceeding 200 h.

Keywords

deep reconstruction / Fe substitution / nickel sulfide / oxygen evolution reaction / Zn–air battery

References

[1] W. Guo, F. Gu, Q. Chen, et al., “Photothermal-Boosted Flexible Rechargeable Zinc-Air Battery Based on Ni-Doped Mn₃O₄ With Excellent Low-Temperature Adaptability,” Carbon Energy 6, no. 11 (2024): e567.

[2] Y. Zhong, Y. Zhang, J. Wang, et al., “Advancing Extreme-Temperature-Tolerant Zinc-Air Batteries Through Photothermal Transition Metal Sulfide Heterostructures,” Energy & Environmental Science 18, no. 2 (2025): 991–1001.

[3] C. Yang, R. Jin, Z. Liu, et al., “Self-Supported N-Doped Carbon-Coupled Ni–Co Binary Nanoparticle Electrodes Derived From Bionic Design of Wood Cell Walls for Durable Overall Water Splitting,” Journal of Materials Chemistry A 12, no. 47 (2024): 33222–33232.

[4] F. Gu, W. Guo, Y. Yuan, et al., “External Field-Responsive Ternary Non-Noble Metal Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries,” Advanced Materials 36, no. 19 (2024): 2313096.

[5] N. Zhang, Y. Hu, L. An, et al., “Surface Activation and Ni-S Stabilization in NiO/NiS₂ for Efficient Oxygen Evolution Reaction,” Angewandte Chemie International Edition 61, no. 35 (2022): e202207217.

[6] Z. Du, Z. Meng, H. Sun, et al., “Exploring the Role of Iron in Fe₅Ni₄S₈ Toward Oxygen Evolution Through Modulation of Electronic Orbital Occupancy,” Journal of Energy Chemistry 92 (2024): 52–62.

[7] X. Liu, J. Wang, H. Liao, et al., “Cationic Oxidative Leaching Engineering Modulated In Situ Self-Reconstruction of Nickel Sulfide for Superior Water Oxidation,” Nano Letters 23, no. 11 (2023): 5027–5034.

[8] L. Gao, X. Cui, C. D. Sewell, J. Li, and Z. Lin, “Recent Advances in Activating Surface Reconstruction for the High-Efficiency Oxygen Evolution Reaction,” Chemical Society Reviews 50, no. 15 (2021): 8428–8469.

[9] X. Liu, K. Ni, B. Wen, et al., “Deep Reconstruction of Nickel-Based Precatalysts for Water Oxidation Catalysis,” ACS Energy Letters 4, no. 11 (2019): 2585–2592.

[10] Y. Zeng, M. Zhao, Z. Huang, et al., “Surface Reconstruction of Water Splitting Electrocatalysts,” Advanced Energy Materials 12, no. 33 (2022): 2201713.

[11] A. Negrea, A. Gabor, C. M. Davidescu, et al., “Rare Earth Elements Removal From Water Using Natural Polymers,” Scientific Reports 8, no. 1 (2018): 316.

[12] D. Li, W. Wan, Z. Wang, et al., “Self-Derivation and Surface Reconstruction of Fe-Doped Ni₃S₂ Electrode Realizing High-Efficient and Stable Overall Water and Urea Electrolysis,” Advanced Energy Materials 12, no. 39 (2022): 2201913.

[13] S. Zhang, Z. Huang, T. T. Isimjan, D. Cai, and X. Yang, “Accurately Substituting Fe for Ni2 Atom in Ni-MOF With Defect-Rich for Efficient Oxygen Evolution Reaction: Electronic Reconfiguration and Mechanistic Study,” Applied Catalysis, B: Environmental 343 (2024): 123448.

[14] Y. Wu, Y. Li, M. Yuan, et al., “Operando Capturing of Surface Self-Reconstruction of Ni₃S₂/FeNi₂S₄ Hybrid Nanosheet Array for Overall Water Splitting,” Chemical Engineering Journal 427 (2022): 131944.

[15] C. Fang, X. Tang, and Q. Yi, “Adding Fe/Dicyandiamide to Co-MOF to Greatly Improve Its ORR/OER Bifunctional Electrocatalytic Activity,” Applied Catalysis, B: Environmental 341 (2024): 123346.

[16] L. Zheng, Y. Zhong, J. Cao, et al., “Modulation of Electronic Synergy to Enhance the Intrinsic Activity of Fe₅Ni₄S₈ Nanosheets in Restricted Space Carbonized Wood Frameworks for Efficient Oxygen Evolution Reaction,” Small 20, no. 21 (2024): 2308928.

[17] Y. Huang, L.-W. Jiang, H. Liu, and J.-J. Wang, “Electronic Structure Regulation and Polysulfide Bonding of Co-Doped (Ni, Fe)_1+XS Enable Highly Efficient and Stable Electrocatalytic Overall Water Splitting,” Chemical Engineering Journal 441 (2022): 136121.

[18] S. Huang, Y. Meng, S. He, et al., “N-, O-, and S-Tridoped Carbon-Encapsulated Co₉S₈ Nanomaterials: Efficient Bifunctional Electrocatalysts for Overall Water Splitting,” Advanced Functional Materials 27, no. 17 (2017): 1606585.

[19] Q. Wang, J. Su, H. Chen, et al., “Highly Conductive Nitrogen-Doped Sp²/Sp³ Hybrid Carbon as a Conductor-Free Charge Storage Host,” Advanced Functional Materials 32, no. 51 (2022): 2209201.

[20] L. Gao, X. Cui, Z. Wang, et al., “Operando Unraveling Photothermal-Promoted Dynamic Active-Sites Generation in NiFe₂O₄ for Markedly Enhanced Oxygen Evolution,” Proceedings of the National Academy of Sciences of the United States of America 118, no. 7 (2021): e2023421118.

[21] S.-W. Wu, S.-Q. Liu, X.-H. Tan, W.-Y. Zhang, K. Cadien, and Z. Li, “Ni₃S₂-Embedded NiFe LDH Porous Nanosheets With Abundant Heterointerfaces for High-Current Water Electrolysis,” Chemical Engineering Journal 442 (2022): 136105.

[22] Y. Li, Y. Wu, M. Yuan, et al., “Operando Spectroscopies Unveil Interfacial FeOOH Induced Highly Reactive β-Ni(Fe)OOH for Efficient Oxygen Evolution,” Applied Catalysis, B: Environmental 318 (2022): 121825.

[23] B. Wu, S. Gong, Y. Lin, et al., “A Unique NiOOH@FeOOH Heteroarchitecture for Enhanced Oxygen Evolution in Saline Water,” Advanced Materials 34, no. 43 (2022): 2108619.

[24] X. He, P. Du, G. Yu, et al., “High-Performance Hydrogen Evolution Reaction Catalytic Electrodes by Liquid Joule-Heating Growth,” Small Methods 7, no. 11 (2023): 2300544.

[25] N. Zhang, X. Feng, D. Rao, et al., “Lattice Oxygen Activation Enabled by High-Valence Metal Sites for Enhanced Water Oxidation,” Nature Communications 11, no. 1 (2020): 4066.

[26] X. Meng, J. Han, L. Lu, G. Qiu, Z. L. Wang, and C. Sun, “Fe²⁺-Doped Layered Double (Ni,Fe) Hydroxides as Efficient Electrocatalysts for Water Splitting and Self-Powered Electrochemical Systems,” Small 15, no. 41 (2019): 1902551.

[27] M. Cai, Q. Zhu, X. Wang, et al., “Formation and Stabilization of NiOOH by Introducing α-FeOOH in LDH: Composite Electrocatalyst for Oxygen Evolution and Urea Oxidation Reactions,” Advanced Materials 35, no. 7 (2023): 2209338.

[28] Z.-P. Wu, S. Zuo, Z. Pei, et al., “Operando Unveiling the Activity Origin via Preferential Structural Evolution in Ni-Fe (Oxy)Phosphides for Efficient Oxygen Evolution,” Science Advances 11, no. 10 (2025): eadu5370.

[29] J. Zhang, Y. Ye, B. Wei, et al., “Unveiling Anion Induced Surface Reconstruction of Perovskite Oxide for Efficient Water Oxidation,” Applied Catalysis, B: Environmental 330 (2023): 122661.

[30] J. Zhang, Y. Ye, Z. Wang, et al., “Probing Dynamic Self-Reconstruction on Perovskite Fluorides Toward Ultrafast Oxygen Evolution,” Advanced Science 9, no. 27 (2022): 2201916.

[31] R. Chen, Z. Zhang, Z. Wang, et al., “Constructing Air-Stable and Reconstruction-Inhibited Transition Metal Sulfide Catalysts via Tailoring Electron-Deficient Distribution for Water Oxidation,” ACS Catalysis 12, no. 21 (2022): 13234–13246.

[32] W. Tang, K. Teng, W. Guo, et al., “Defect-Engineered Co₃O₄@Nitrogen-Deficient Graphitic Carbon Nitride as an Efficient Bifunctional Electrocatalyst for High-Performance Metal-Air Batteries,” Small 18, no. 27 (2022): 2202194.

[33] Z. Du, Z. Meng, X. Gong, et al., “Rapid Surface Reconstruction of Pentlandite by High-Spin State Iron for Efficient Oxygen Evolution Reaction,” Angewandte Chemie International Edition 63, no. 6 (2024): e202317022.

[34] D. Wu, L. Hu, X. Liu, et al., “Time-Resolved Spectroscopy Uncovers Deprotonation-Induced Reconstruction in Oxygen-Evolution NiFe-Based (Oxy)Hydroxides,” Nature Communications 16, no. 1 (2025): 726.

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2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.