Dynamic Chloride-Ion Adsorption on Ag Nanoparticles and Carboxylic Acid Ligands: Enabling Highly Stable Industrial-Scale Seawater Oxidation

Abstract

The key to efficient hydrogen production through industrial-scale alkaline seawater electrolysis lies in the catalyst's stability at current densities ≥ 500 mA cm⁻² and its resistance to chlorine corrosion. Herein, the synthesis of a layered double hydroxide (LDH) of NiFeCo modified with trimesic acid (TA) and silver nanoparticles (denoted as NiFeCo-LDH(TA)@Ag) is reported. The catalyst requires only 330 mV overpotential to achieve the current density of 1 A cm⁻² under industrial conditions (60°C, 6 M KOH + seawater). Specifically, a two-electrode system employing NiFeCo-LDH(TA)@Ag for the anode and commercial Ni foam for the cathode demonstrates excellent durability, operating for over 1300 h without significant performance degradation. Both results from experiments and theoretical calculations reveal that coordination between TA and LDH stabilizes the metal centers and facilitates electron transfer, which decreases the rate-determining step energy barrier (3.07 eV). Furthermore, the preferential dynamic adsorption of Cl⁻ ions on Ag nanoparticles effectively shields active sites from Cl⁻ corrosion. This work provides a practical strategy for developing electrocatalysts that combine high performance and high stability for industrial-scale seawater electrolysis.

Keywords

chlorine corrosion resistance / electrocatalysts / seawater electrolysis

References

[1] B. S. Zainal, P. J. Ker, H. Mohamed, et al., “Recent Advancement and Assessment of Green Hydrogen Production Technologies,” Renewable and Sustainable Energy Reviews 189 (2023): 113941, https://doi.org/10.1016/j.rser.2023.113941.

[2] S. P. Shelake, D. N. Sutar, B. M. Abraham, T. Banerjee, A. V. S. Sainath, and U. Pal, “Emerging Photoreforming Process to Hydrogen Production: A Future Energy,” Advanced Functional Materials 34, no. 40 (2024): 2403795, https://doi.org/10.1002/adfm.202403795.

[3] W. Xiao, Y. Chen, Q. Zhao, D. Bukhvalov, C. Wang, and X. Yang, “Constructing the Synergistic Active Sites of Nickel Bicarbonate Supported Pt Hierarchical Nanostructure for Efficient Hydrogen Evolution Reaction,” Chinese Chemical Letters 35, no. 12 (2024): 110176, https://doi.org/10.1016/j.cclet.2024.110176.

[4] X. Liu, J. Chi, H. Mao, and L. Wang, “Principles of Designing Electrocatalyst to Boost Reactivity for Seawater Splitting,” Advanced Energy Materials 13, no. 31 (2023): 2301438, https://doi.org/10.1002/aenm.202301438.

[5] W. Xu, T. Ma, H. Chen, et al., “Scalable Fabrication of Cu₂S@NiS@Ni/NiMo Hybrid Cathode for High-Performance Seawater Electrolysis,” Advanced Functional Materials 33, no. 37 (2023): 2302263, https://doi.org/10.1002/adfm.202302263.

[6] P. Zhou, P. Niu, J. Liu, et al., “Anodized Steel: The Most Promising Bifunctional Electrocatalyst for Alkaline Water Electrolysis in Industry,” Advanced Functional Materials 32, no. 26 (2022): 2202068, https://doi.org/10.1002/adfm.202202068.

[7] H. Sun, X. Xu, H. Kim, W. Jung, W. Zhou, and Z. Shao, “Electrochemical Water Splitting: Bridging the Gaps Between Fundamental Research and Industrial Applications,” Energy & Environmental Materials 6, no. 5 (2022): e12441, https://doi.org/10.1002/eem2.12441.

[8] S. Zuo, Z. P. Wu, H. Zhang, and X. W. Lou, “Operando Monitoring and Deciphering the Structural Evolution in Oxygen Evolution Electrocatalysis,” Advanced Energy Materials 12, no. 8 (2022): 2103383, https://doi.org/10.1002/aenm.202103383.

[9] Q. Guo, X. Liu, C. Ke, W. Xiao, and X. Yang, “A corrosion-Engineered Transition Metal Multi-Anionic Interface for Efficient Electrocatalysis Toward Overall Water Splitting,” New Journal of Chemistry 47, no. 47 (2023): 21732–21742, https://doi.org/10.1039/d3nj04235a.

[10] X. Wang, X. Zhou, C. Li, et al., “Asymmetric Co-N₃P₁ Trifunctional Catalyst With Tailored Electronic Structures Enabling Boosted Activities and Corrosion Resistance in an Uninterrupted Seawater Splitting System,” Advanced Materials 34, no. 34 (2022): 2204021, https://doi.org/10.1002/adma.202204021.

[11] L. Yu, Q. Zhu, S. Song, et al., “Non-Noble Metal-Nitride Based Electrocatalysts for High-Performance Alkaline Seawater Electrolysis,” Nature Communications 10, no. 1 (2019): 5106, https://doi.org/10.1038/s41467-019-13092-7.

[12] W. Tong, M. Forster, F. Dionigi, et al., “Electrolysis of Low-Grade and Saline Surface Water,” Nature Energy 5, no. 5 (2020): 367–377, https://doi.org/10.1038/s41560-020-0550-8.

[13] W. Xiao, Y. Chen, C. Ke, F. Han, C. Wang, and X. Yang, “Engineering the Heterostructured Ni₉S₈–FeO_x Nanoarrays for Electrocatalytic (Sea)Water Splitting,” ACS Applied Nano Materials 8, no. 1 (2024): 512–523, https://doi.org/10.1021/acsanm.4c05901.

[14] V. R. Jothi, K. Karuppasamy, T. Maiyalagan, H. Rajan, C. Jung, and S. C. Yi, “Corrosion and Alloy Engineering in Rational Design of High Current Density Electrodes for Efficient Water Splitting,” Advanced Energy Materials 10, no. 24 (2020): 1904020, https://doi.org/10.1002/aenm.201904020.

[15] L. Tan, J. Yu, C. Wang, et al., “Partial Sulfidation Strategy to NiFe-LDH@FeNi₂S₄ Heterostructure Enable High-Performance Water/Seawater Oxidation,” Advanced Functional Materials 32, no. 29 (2022): 2200951, https://doi.org/10.1002/adfm.202200951.

[16] H. Zhang, Z. Bi, P. Sun, et al., “Dense Crystalline/Amorphous Phosphides/Oxides Interfacial Sites for Enhanced Industrial-Level Large Current Density Seawater Oxidation,” ACS Nano 17, no. 16 (2023): 16008–16019, https://doi.org/10.1021/acsnano.3c04519.

[17] F. Dionigi, J. Zhu, Z. Zeng, et al., “Intrinsic Electrocatalytic Activity for Oxygen Evolution of Crystalline 3d-Transition Metal Layered Double Hydroxides,” Angewandte Chemie International Edition 60, no. 26 (2021): 14446–14457, https://doi.org/10.1002/anie.202100631.

[18] Y. Tang, Q. Liu, L. Dong, H. B. Wu, and X.-Y. Yu, “Activating the Hydrogen Evolution and Overall Water Splitting Performance of NiFe LDH by Cation Doping and Plasma Reduction,” Applied Catalysis B: Environment and Energy 266 (2020): 118627, https://doi.org/10.1016/j.apcatb.2020.118627.

[19] H. Sun, L. Chen, Y. Lian, et al., “Topotactically Transformed Polygonal Mesopores on Ternary Layered Double Hydroxides Exposing Under-Coordinated Metal Centers for Accelerated Water Dissociation,” Advanced Materials 32, no. 52 (2020): 2006784, https://doi.org/10.1002/adma.202006784.

[20] L. Chunfa, B. Haoyun, F. Jinxian, et al., “Electrodeposited Ternary Metal (Oxy)Hydroxide Achieves Highly Efficient Alkaline Water Electrolysis over 1000 H Under Industrial Conditions,” Carbon Energy 7, no. 6 (2025): e684, https://doi.org/10.1002/cey2.684.

[21] R. Chen, S. F. Hung, D. Zhou, et al., “Layered Structure Causes Bulk NiFe Layered Double Hydroxide Unstable in Alkaline Oxygen Evolution Reaction,” Advanced Materials 31, no. 41 (2019): 1903909, https://doi.org/10.1002/adma.201903909.

[22] C. Kuai, Z. Xu, C. Xi, et al., “Phase Segregation Reversibility in Mixed-Metal Hydroxide Water Oxidation Catalysts,” Nature catalysis 3, no. 9 (2020): 743–753, https://doi.org/10.1038/s41929-020-0496-z.

[23] L. Peng, N. Yang, Y. Yang, et al., “Atomic Cation-Vacancy Engineering of NiFe-Layered Double Hydroxides for Improved Activity and Stability Towards the Oxygen Evolution Reaction,” Angewandte Chemie International Edition 60, no. 46 (2021): 24612–24619, https://doi.org/10.1002/anie.202109938.

[24] W. Fengyu, T. Fenyang, L. Menggang, et al., “Engineering Lattice Oxygen Regeneration of NiFe Layered Double Hydroxide Enhances Oxygen Evolution Catalysis Durability,” Angewandte Chemie International Edition 64, no. 1 (2024): e202413250, https://doi.org/10.1002/anie.202413250.

[25] H. Yihang, S. Tianyang, W. Zhaohui, et al., “Coordination Stabilization of Fe by Porphyrin-Intercalated NiFe-LDH Under Industrial-Level Alkaline Conditions for Long-Term Electrocatalytic Water Oxidation,” Advanced Functional Materials 35, no. 3 (2024): 2413533, https://doi.org/10.1002/adfm.202413533.

[26] X. Lin, Z. Wang, S. Cao, et al., “Bioinspired Trimesic Acid Anchored Electrocatalysts With Unique Static and Dynamic Compatibility for Enhanced Water Oxidation,” Nature Communications 14, no. 1 (2023): 6714, https://doi.org/10.1038/s41467-023-42292-5.

[27] C. F. Li, J. W. Zhao, L. J. Xie, et al., “Surface-Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal-Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction,” Angewandte Chemie International Edition 60, no. 33 (2021): 18129–18137, https://doi.org/10.1002/anie.202104148.

[28] R. Zhu, J. Ding, Y. Xu, J. Yang, Q. Xu, and H. Pang, “π-Conjugated Molecule Boosts Metal-Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts,” Small 14, no. 50 (2018): 1803576, https://doi.org/10.1002/smll.201803576.

[29] F. Chen, X.-Y. Zhong, J. Ding, et al., “Trimesic Acid Modified Copper-Cobalt Layered Double Hydroxide Nanosheets Boost Electrocatalytic Reduction of Nitrate to Ammonia,” Journal of Colloid and Interface Science 701 (2025): 138664, https://doi.org/10.1016/j.jcis.2025.138664.

[30] L. Wu, L. Yu, F. Zhang, et al., “Heterogeneous Bimetallic Phosphide Ni₂P-Fe₂P as an Efficient Bifunctional Catalyst for Water/Seawater Splitting,” Advanced Functional Materials 31, no. 1 (2020): 2006484, https://doi.org/10.1002/adfm.202006484.

[31] Q. Sha, S. Wang, L. Yan, et al., “10,000-h-Stable Intermittent Alkaline Seawater Electrolysis,” Nature 639, no. 8054 (2025): 1–8, https://doi.org/10.1038/s41586-025-08610-1.

[32] W. Hao, X. Ma, L. Wang, et al., “Surface Corrosion-Resistant and Multi-Scenario MoNiP Electrode for Efficient Industrial-Scale Seawater Splitting,” Advanced Energy Materials 15, no. 5 (2024): 2403009, https://doi.org/10.1002/aenm.202403009.

[33] L. Yu, L. Wu, B. Mcelhenny, et al., “Ultrafast Room-Temperature Synthesis of Porous S-Doped Ni/Fe (Oxy)Hydroxide Electrodes for Oxygen Evolution Catalysis in Seawater Splitting,” Energy & Environmental Science 13, no. 10 (2020): 3439–3446, https://doi.org/10.1039/d0ee00921k.

[34] T. Ma, W. Xu, B. Li, et al., “The Critical Role of Additive Sulfate for Stable Alkaline Seawater Oxidation on Nickel-Based Electrodes,” Angewandte Chemie International Edition 133, no. 42 (2021): 22922–22926, https://doi.org/10.1002/ange.202110355.

[35] Y. Kuang, M. J. Kenney, Y. Meng, et al., “Solar-Driven, Highly Sustained Splitting of Seawater Into Hydrogen and Oxygen Fuels,” Proceedings of the National Academy of Sciences of the United States of America 116, no. 14 (2019): 6624–6629, https://doi.org/10.1073/pnas.1900556116.

[36] X. Shen, H. Li, T. Ma, et al., “Construction of Heterojunction-Rich Metal Nitrides Porous Nanosheets Electrocatalyst for Alkaline Water/Seawater Splitting at Large Current Density,” Small 20, no. 30 (2024): 2310535, https://doi.org/10.1002/smll.202310535.

[37] X. Duan, Q. Sha, P. Li, et al., “Dynamic Chloride Ion Adsorption on Single Iridium Atom Boosts Seawater Oxidation Catalysis,” Nature Communications 15, no. 1 (2024): 1973, https://doi.org/10.1038/s41467-024-46140-y.

[38] Q. Niu, F. Y. Gao, X. Sun, Y. Zheng, and S. Z. Qiao, “Chloride-Mediated Electron Buffering on Ni-Fe Anodes for Ampere-Level Alkaline Seawater Electrolysis,” Advanced Functional Materials 35, no. 36 (2025): 2504872, https://doi.org/10.1002/adfm.202504872.

[39] M. Gong, Y. Li, H. Wang, et al., “An Advanced Ni-Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation,” Journal of the American Chemical Society 135, no. 23 (2013): 8452–8455, https://doi.org/10.1021/ja4027715.

[40] C. Ning, J. Yang, S. Bai, et al., “An Efficient Intercalation Supramolecular Structure for Photocatalytic CO₂ Reduction to Ethylene Under Visible Light,” Advanced Functional Materials 33, no. 42 (2023): 2300365, https://doi.org/10.1002/adfm.202300365.

[41] X. Lin, S. Cao, X. Chen, et al., “Two Birds With One Stone: Contemporaneously Boosting OER Activity and Kinetics for Layered Double Hydroxide Inspired by Photosystem II,” Advanced Functional Materials 32, no. 27 (2022): 2202072, https://doi.org/10.1002/adfm.202202072.

[42] H. Chen, R. T. Gao, H. Chen, Y. Yang, L. Wu, and L. Wang, “Ruthenium and Silver Synergetic Regulation NiFe LDH Boosting Long-Duration Industrial Seawater Electrolysis,” Advanced Functional Materials 34, no. 25 (2024): 2315674, https://doi.org/10.1002/adfm.202315674.

[43] Y.-J. Wu, J. Yang, T.-X. Tu, et al., “Evolution of Cationic Vacancy Defects: A Motif for Surface Restructuration of OER Precatalyst,” Angewandte Chemie International Edition 60, no. 51 (2021): 26829–26836, https://doi.org/10.1002/anie.202112447.

[44] Q. Zhang, G. Zhang, Y. Huang, et al., “Surface-Modified LDH Nanosheets With High Dispersibility in Oil for Friction and Wear Reduction,” ACS Applied Materials & Interfaces 16, no. 4 (2024): 5316–5325, https://doi.org/10.1021/acsami.3c17322.

[45] 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, no. 1 (2023): 1873, https://doi.org/10.1038/s41467-023-37091-x.

[46] Y. Wang, M. Qiao, Y. Li, and S. Wang, “Tuning Surface Electronic Configuration of NiFe LDHs Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction,” Small 14, no. 17 (2018): 1800136, https://doi.org/10.1002/smll.201800136.

[47] Z. Xu, Y. Ying, G. Zhang, et al., “Engineering NiFe Layered Double Hydroxide by Valence Control and Intermediate Stabilization Toward the Oxygen Evolution Reaction,” Journal of Materials Chemistry A 8, no. 48 (2020): 26130–26138, https://doi.org/10.1039/d0ta08815c.

[48] Y. Lin, H. Wang, C. K. Peng, et al., “Co-Induced Electronic Optimization of Hierarchical NiFe LDH for Oxygen Evolution,” Small 16, no. 38 (2020): 2002426, https://doi.org/10.1002/smll.202002426.

[49] Y.-J. Ko, M. H. Han, H. Kim, et al., “Unraveling Ni-Fe 2D Nanostructure With Enhanced Oxygen Evolution via in Situ and Operando Spectroscopies,” Chem Catalysis 2, no. 9 (2022): 2312–2327, https://doi.org/10.1016/j.checat.2022.07.016.

[50] H. Lei, L. Ma, Q. Wan, et al., “Promoting Surface Reconstruction of NiFe Layered Double Hydroxide for Enhanced Oxygen Evolution,” Advanced Energy Materials 12, no. 48 (2022): 2202522, https://doi.org/10.1002/aenm.202202522.

[51] J. Zhang, J. Liu, L. Xi, et al., “Single-Atom Au/NiFe Layered Double Hydroxide Electrocatalyst: Probing the Origin of Activity for Oxygen Evolution Reaction,” Journal of the American Chemical Society 140, no. 11 (2018): 3876–3879, https://doi.org/10.1021/jacs.8b00752.

[52] L. Yang, Z. Guo, J. Huang, et al., “Vertical Growth of 2D Amorphous FePO₄ Nanosheet on Ni Foam: Outer and Inner Structural Design for Superior Water Splitting,” Advanced Materials 29, no. 46 (2017): 1704574, https://doi.org/10.1002/adma.201704574.

RIGHTS & PERMISSIONS

2026 The Author(s). EcoEnergy published by John Wiley & Sons Australia, Ltd on behalf of China Chemical Safety Association.