Constructing the Ni₄N/Ni₃N Heterointerface of the Bicontinuous Ni₄N/Ni₃N/NiO/CFs Catalyst With Pore Connectivity Effects for Electrocatalytic Hydrogen Generation

Abstract

Designing and fabricating well-defined heterointerface catalysts with high electrocatalytic performance for the hydrogen evolution reaction (HER) remains a huge challenge. Here, the bicontinuous nano-heterostructure consisting of ultrathin Ni₄N/Ni₃N particles on hollow tubular carbon fibers was fabricated, and it exhibits superior catalytic activity with a very low overpotential of 75 mV@10 mA cm⁻² for HER and stable performance for over 50 h. Theoretical calculation results revealed that the built-in interfacial electric field (BIEF) is formed due to the distinct lattice arrangements and uneven charge distribution in biphasic metal nitrides. The BIEF promotes the electron localization around the interface and enables high valence Ni and more exposed binding sites on the surface of Ni₄N/Ni₃N/NiO/CFs to accelerate the HER. Meanwhile, the pore connectivity effects facilitate the full exposure of the optimized Ni₄N/Ni₃N heterointerface, which possesses enhanced intrinsic catalytic activity as active sites. Moreover, the pore connectivity microstructure of the Ni₄N/Ni₃N/NiO/CFs is conceptualized and verified through the utilization of three-dimensional tomograph reconstruction technology. This study offers new insights into constructing heterostructure interfacial catalysts with three-dimensional spatial precision and provides strong references for practical applications in electrocatalytic hydrogen generation techniques.

Keywords

built-in interfacial electric field / Ni4N/Ni3N heterostructure / pore connectivity effects / theoretical calculation / three-dimensional tomograph reconstruction

References

[1] H. Zhu, Y. Wang, Z. Jiang, B. Deng, Y. Xin, and Z. J. Jiang, “Defect Engineering Promoted Ultrafine Ir Nanoparticle Growth and Sr Single-Atom Adsorption on TiO₂ Nanowires to Achieve High-Performance Overall Water Splitting in Acidic Media,” Advanced Energy Materials 14 (2024): 202303987.

[2] T. Wu, E. Song, S. Zhang, et al., “Engineering Metallic Heterostructure Based on Ni₃N and 2M-MoS₂ for Alkaline Water Electrolysis With Industry-Compatible Current Density and Stability,” Advanced Materials 34 (2022): 202108505.

[3] H. Ze, Z. L. Yang, M. L. Li, et al., “In Situ Probing the Structure Change and Interaction of Interfacial Water and Hydroxyl Intermediates on Ni(OH)₂ Surface Over Water Splitting,” Journal of the American Chemical Society 146 (2024): 12538–12546.

[4] M. Xi, A.-R. Chen, L.-F. Yang, et al., “Effective Hydrogen Evolution Enabled by Heterogeneous Interface Engineering in Bimetallic Sulfide With MoNi Alloy,” Rare Metals 44 (2025): 3094–3106.

[5] P. Kuang, Z. Ni, B. Zhu, Y. Lin, and J. Yu, “Modulating the d-Band Center Enables Ultrafine Pt₃Fe Alloy Nanoparticles for pH-Universal Hydrogen Evolution Reaction,” Advanced Materials 35 (2023): 202303030.

[6] J. Chen, Y. Zhao, S. Zhao, et al., “Heterogeneous Bimetallic Oxides/Phosphides Nanorod With Upshifted d Band Center for Efficient Overall Water Splitting,” Chinese Chemical Letters 35 (2024): 109268.

[7] Z. Tu, C. Zhao, T. Munawar, et al., “Boosting the HER Activity of Three-Phase A-MoS_x/Ni₃S₂/Ni₃N Heterojunction via Simultaneous Structural Control and Heterointerface Engineering,” Chemical Engineering Journal 510 (2025): 161077.

[8] D. D. Alemayehu, M.-C. Tsai, M.-H. Tsai, et al., “Heterogeneous Interfaces of Ni₃Se₄ Nanoclusters Decorated on a Ni₃N Surface Enhance Efficient and Durable Hydrogen Evolution Reactions in Alkaline Electrolyte,” Journal of the American Chemical Society 147 (2025): 16047–16059.

[9] D. Wang, C. Zhang, J. Hu, T. Zhuang, and Z. Lv, “Nitriding-Reduction Fabrication of Coralloid CoN/Ni/NiO for Efficient Electrocatalytic Overall Water Splitting,” Journal of Colloid and Interface Science 655 (2024): 217–225.

[10] M. Luo, J. Yang, X. Li, M. Eguchi, Y. Yamauchi, and Z.-L. Wang, “Insights Into Alloy/Oxide or Hydroxide Interfaces in Ni–Mo-Based Electrocatalysts for Hydrogen Evolution Under Alkaline Conditions,” Chemical Science 14 (2023): 3400–3414.

[11] W. Zhang, C. Li, J.-Y. Ji, et al., “Tailorable Carbon Cloth Electrodes Covered With Heterostructured Co/CoO/CoN Interfaces for Scalable Electrocatalytic Overall Water Splitting,” Chemical Engineering Journal 461 (2023): 141937.

[12] W. Peng, Z. Wang, R. Lu, et al., “Artificial Heterointerfaces of Defect-Rich Ni and Amorphous/Crystalline MoN Enable Efficient Hydrogen Evolution Reaction,” Chemical Engineering Journal 457 (2023): 141173.

[13] R. Balaji, T. T. Nguyen, Q. P. Ngo, N. H. Kim, and J. H. Lee, “Unveiling the Synergistic Mechanism of Atomic Rh on Couple Phase CoSe₂/CoSeO₃ for Enhanced Alkaline Water Electrolysis Devices,” Advanced Functional Materials 34 (2024): 202410672.

[14] L. Cui, Y. Wang, K. Yu, Y. Ma, and B. Zhou, “A Multi-Active Site Subnano Heterostructures Catalyst Grown In Situ POM and Fe_0.2Ni_0.8Co₂O₄ Onto Nickel Foam Toward Efficient Electrocatalytic Overall Water Splitting,” Advanced Functional Materials 34 (2024): 202108968.

[15] J. Jiang, Y. Qiu, H. Dong, et al., “Enhancing Hydrogen Evolution by Heterointerface Engineering of Ni/MoN Catalysts,” Journal of Colloid and Interface Science 686 (2025): 681–690.

[16] M. Zhou, B. Jin, W. Kong, et al., “Dual Polarization of Ni Sites at Vo_x-Ni₃N Interface Boosts Ethanol Oxidation Reaction,” Advanced Science 11 (2024): 2407473.

[17] P. Zhai, C. Wang, Y. Zhao, et al., “Regulating Electronic States of Nitride/Hydroxide to Accelerate Kinetics for Oxygen Evolution at Large Current Density,” Nature Communications 14 (2023): 1873.

[18] C. Pi, D. Leng, X. Zhang, et al., “Crystal Facet-Induced Reconstruction of MoN-Supported Co Pre-Catalysts for Optimized Active Sites and Enhanced Alkaline Hydrogen Evolution,” Journal of Colloid and Interface Science 687 (2025): 461–470.

[19] K. Deng, X. Liu, P. Liu, X. Lv, W. Tian, and J. Ji, “Enhanced Adsorption Kinetics and Capacity of a Stable CeF₃@Ni₃N Heterostructure for Methanol Electro-Reforming Coupled With Hydrogen Production,” Angewandte Chemie-International Edition 64 (2024): 202416763.

[20] Y. Wei, L. Yi, S. Zhang, et al., “Ni–Mo Nitride Synthesized via Mild Plasma for Efficient Alkaline Hydrogen Evolution Electrocatalysis,” Journal of Materials Chemistry A 12 (2024): 8534–8542.

[21] T. Xiong, J. Li, J. Chandra Roy, et al., “Hetero-Interfacial Nickel Nitride/Vanadium Oxynitride Porous Nanosheets as Trifunctional Electrodes for HER, OER and Sodium Ion Batteries,” Journal of Energy Chemistry 81 (2023): 71–81.

[22] X. Wang, G. Long, B. Liu, et al., “Rationally Modulating the Functions of Ni₃Sn₂-NiSnO_x Nanocomposite Electrocatalysts Towards Enhanced Hydrogen Evolution Reaction,” Angewandte Chemie International Edition 62 (2023): 202301562.

[23] A. Tewary, S. Mandal, Z. Alam, A. S. K. Sinha, and U. Ojha, “Scalable Green Synthesis of Ni₃N-Encapsulated NC-Layered FeOOH Heterostructures: Bifunctional Electrodes for Sustainable Electrocatalytic Seawater Splitting,” ACS Sustainable Chemistry & Engineering 11 (2023): 6556–6566.

[24] H. Wang, Y. Jiao, G. Zhang, et al., “Superaerophobic Ni₃N/Ni@W₂N₃ Multi-Heterointerfacial Nanoarrays for Efficient Alkaline Electrocatalytic Hydrogen Evolution Reaction,” Chemical Engineering Journal 497 (2024): 154776.

[25] F. Ma, S. Wang, X. Gong, et al., “Highly Efficient Electrocatalytic Hydrogen Evolution Coupled With Upcycling of Microplastics in Seawater Enabled via Ni₃N/W₅N₄ Janus Nanostructures,” Applied Catalysis, B: Environmental 307 (2022): 121198.

[26] M. Li, X. Wu, K. Liu, et al., “Nitrogen Vacancies Enriched Ce-Doped Ni₃N Hierarchical Nanosheets Triggering Highly-Efficient Urea Oxidation Reaction in Urea-Assisted Energy-Saving Electrolysis,” Journal of Energy Chemistry 69 (2022): 506–515.

[27] X. Liu, Z. Fang, D. Xiong, et al., “Upcycling PET in Parallel With Energy-Saving H₂ Production via Bifunctional Nickel-Cobalt Nitride Nanosheets,” Nano Research 16 (2023): 4625–4633.

[28] X. Liao, Z. Huang, W. Zhang, Y. Meng, L. Yang, and Q. Gao, “Cr-Doping Promoted Surface Reconstruction of Ni₃N Electrocatalysts Toward Efficient Overall Water Splitting,” Journal of Colloid and Interface Science 674 (2024): 1048–1057.

[29] J. Li, W. Zhou, S. Yu, et al., “Cu-Induced Interface Engineering of NiCu/Ni₃N Heterostructures for Enhanced Alkaline Hydrogen Oxidation Reaction,” Chinese Journal of Catalysis 67 (2024): 186–193.

[30] P. Zhou, G. Zhai, X. Lv, et al., “Boosting the Electrocatalytic HER Performance of Ni₃N-V₂O₃ via the Interface Coupling Effect,” Applied Catalysis, B: Environmental 283 (2021): 119590.

[31] J. Li, W. Zhou, S. Yu, et al., “Cu-Induced Interface Engineering of NiCu/Ni₃N Heterostructures for Enhanced Alkaline Hydrogen Oxidation Reaction,” Chinese Journal of Catalysis 67 (2024): 186–193.

[32] H. Wang, Y. Jiao, G. Zhang, et al., “Superaerophobic Ni₃N/Ni@W₂N₃ Multi-Heterointerfacial Nanoarrays for Efficient Alkaline Electrocatalytic Hydrogen Evolution Reaction,” Chemical Engineering Journal 497 (2024): 154776.

[33] H. W. Huang, L. L. Xu, S. W. Zuo, et al., “Pioneering Built-in Interfacial Electric Field for Enhanced Anion Exchange Membrane Water Electrolysis,” Angewandte Chemie-International Edition 64 (2024): 202414647.

[34] C. Cai, K. Liu, L. Zhang, et al., “Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction,” Angewandte Chemie-International Edition 62 (2023): 202300873.

[35] S. Liu, Z. Li, Y. Chang, et al., “Substantial Impact of Built-in Electric Field and Electrode Potential on the Alkaline Hydrogen Evolution Reaction of Ru-CoP Urchin Arrays,” Angewandte Chemie International Edition 63 (2024): 202400069.

[36] X. Y. He, Y. H. Tian, D. J. Deng, et al., “Engineering Antiperovskite Ni₄N/VN Heterostructure With Improved Intrinsic Interfacial Charge Transfer as a Bifunctional Catalyst for Rechargeable Zinc-Air Batteries,” ACS Sustainable Chemistry & Engineering 9 (2021): 17007–17015.

[37] D. Chen, R. Yu, K. Yu, et al., “Bicontinuous RuO₂ Nanoreactors for Acidic Water Oxidation,” Nature Communications 15 (2024): 3928.

[38] T. Wang, L. Miao, S. Zheng, et al., “Interfacial Engineering of Ni₃N/Mo₂N Heterojunctions for Urea-Assisted Hydrogen Evolution Reaction,” ACS Catalysis 13 (2023): 4091–4100.

[39] J. Wang, Z. Li, Z. Zhu, et al., “Tailoring the Interactions of Heterostructured Ni₄N/Ni₃ZnC_0.7 for Efficient CO₂ Electroreduction,” Journal of Energy Chemistry 75 (2022): 1–7.

[40] Y. Dong, X. Zhang, X. Wang, et al., “Kirkendall Effect Strengthened-Superhydrophilic/Superaerophobic Co-Ni₃N/NF Heterostructure as Electrode Catalyst for High-Current Hydrogen Production,” Journal of Colloid and Interface Science 636 (2023): 657–667.

[41] 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 (2024): 33222–33232.

[42] H. Liu, P. Wang, X. Qi, et al., “Accumulated Charge Density at the Interface Boosts the Urea Oxidation Reaction Activity of Ni₃N/Ni₃S₂ Heterointerface,” Chemical Engineering Journal 491 (2024): 152160.

[43] Q. Zhou, J. Wang, G. Jin, H. Liu, and C. Wang, “Enhanced Surface Reconstruction of V-Doped Ni₃N Driven by Strong OH Adsorption to Boost 5-Hydroxymethylfurfural Electrooxidation for Energy-Saving H₂ Production,” Journal of Materials Chemistry A 12 (2024): 12475–12486.

[44] J. Chen, Z. Hu, Y. Ou, et al., “Interfacial Engineering Regulated by CeO_x to Boost Efficiently Alkaline Overall Water Splitting and Acidic Hydrogen Evolution Reaction,” Journal of Materials Science & Technology 120 (2022): 129–138.

[45] L. Xiao, Y. Wang, T. Fu, et al., “Facile Synthesis of Ultrafine Iron-Cobalt (FeCo) Nanocrystallite-Embedded Boron/Nitrogen-Codoped Porous Carbon Nanosheets: Accelerated Water Splitting Catalysts,” Journal of Colloid and Interface Science 654 (2024): 150–163.

[46] C. Lyu, C. Cao, J. Cheng, et al., “Interfacial Electronic Structure Modulation of Ni₂P/Ni₅P₄ Heterostructure Nanosheets for Enhanced pH-Universal Hydrogen Evolution Reaction Performance,” Chemical Engineering Journal 464 (2023): 142538.

[47] G. Zhao, Y. Jiang, S. X. Dou, W. Sun, and H. Pan, “Interface Engineering of Heterostructured Electrocatalysts Towards Efficient Alkaline Hydrogen Electrocatalysis,” Science Bulletin 66 (2021): 85–96.

[48] L. Yan, J. Liang, D. Song, X. Li, and H. Li, “Modulation of Charge Redistribution in Heterogeneous NiO-Ni₃Se₄ Nanosheet Arrays for Advanced Water Electrolysis,” Advanced Functional Materials 34 (2024): 202308345.

[49] L. Yang, H. Liu, Y. Li, et al., “Customizing Bonding Affinity With Multi-Intermediates via Interfacial Electron Capture to Boost Hydrogen Evolution in Alkaline Water Electrolysis,” Angewandte Chemie International Edition 64 (2025): 202414518.

[50] W. Zhang, L. Yang, Z. Li, et al., “Regulating Hydrogen/Oxygen Species Adsorption via Built-in Electric Field -Driven Electron Transfer Behavior at the Heterointerface for Efficient Water Splitting,” Angewandte Chemie International Edition 63 (2024): 202400888.

[51] X. Mu, Y. Yuan, M. Yu, et al., “Robust Water/Seawater-Electrolysis Hydrogen Production at Industrial-Scale Current Densities by Modulating Built-in-Outer Electric Field of Catalytic Substance,” Nano Energy 131 (2024): 110216.

[52] H. Huang, L. Xu, S. Zuo, et al., “Pioneering Built-in Interfacial Electric Field for Enhanced Anion Exchange Membrane Water Electrolysis,” Angewandte Chemie International Edition 64 (2025): 202414647.

[53] P. Li, Y. Huang, Q. Huang, R. Chen, J. Li, and S. Tian, “Cobalt Phosphide With Porous Multishelled Hollow Structure Design Realizing Promoted Ammonia Borane Dehydrogenation: Elucidating Roles of Architectural and Electronic Effect,” Applied Catalysis, B: Environmental 313 (2022): 121444.

[54] J. Li, C. Yin, S. Wang, B. Zhang, and L. Feng, “Built-in Electrophilic/Nucleophilic Domain of Nitrogen-Doped Carbon Nanofiber-Confined Ni₂P/Ni₃N Nanoparticles for Efficient Urea-Containing Water-Splitting Reactions,” Chemical Science 15 (2024): 13659–13667.

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