Abstract
Developing active and stable electrocatalysts for the chlorine evolution reaction (CER) is critical for chlor-alkali processes but remains challenging. Here we introduce ultrafine high-entropy alloy nanowires (UF-HEANWs) enriched with atomic steps as efficient CER catalysts for direct chlorine electrosynthesis from seawater. A seawater flow electrolyser equipped with UF-HEANW anodes achieves 98.1% CER selectivity at an industrial-scale current density of 10 kA m−2, maintaining continuous operation for over 5,500 h. Operando studies reveal that atomic steps in lattice-distorted UF-HEANWs create corner-edge electronic heterogeneity, triggering the in situ generation of high-valent Pt–O sites with localized electronic states and unsaturated coordination. These dynamic active structures enhance chloride adsorption and chlorine desorption, leading to improved activity and selectivity during CER. A techno-economic analysis shows that costs are reduced by 32.8% versus the chlor-alkali industry, with 51.3% less electricity used during electrolysis via high-entropy alloy anodes and 83.1% lower feedstock costs from seawater replacement.

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Acknowledgements
S.Z. is thankful for support from the National Key R&D Program of China (grant no. 2024YFA1211100) and the National Natural Science Foundation of China (grant no. 22373027). Yongchao Yang is thankful for financial support from the FH Loxton Fellowship. J.A.Y. acknowledges financial support from the Australian Research Council (grant no. DE250101071) and high-performance computational support from the National Computing Infrastructure Australia. R.D.T. would like to acknowledge support from the Australian Research Council (grant no. CE230100032). We acknowledge the European Synchrotron Radiation Facility for the provision of synchrotron radiation facilities for HE-XRD/PDF measurements at the ID11 beamline. XAS measurements were performed at the XAS and SXR beamlines of the Australian Synchrotron, part of ANSTO. HAXPES survey was carried out on the Spectroscopy Soft and Tender 2 (SST-2) beamline at the National Synchrotron Light Source II. We acknowledge the Mark Wainwright Analytical Centre and Microscopy Australia for support of facilities at the Electron Microscope Unit (EMU) at UNSW. The scientific and technical support from EMU at UNSW in Sydney is appreciated.
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S.Z. proposed the research direction and supervised the research project. Yongchao Yang performed the material design, synthesis and electrochemical experiments, and drafted and revised the whole manuscript. S.C. and R.D.T. performed HRTEM, HAADF-STEM and EDS characterizations. Yuwei Yang and N.M.B. performed XAS, HE-XRD and HAXPES measurements. Yongchao Yang and X.S. conducted the techno-economic analysis. T.Z. conducted in situ FTIR characterization. J.A.Y. conducted the theoretical calculations. Yongchao Yang and S.Z. discussed the research results. All authors assisted during the preparation of the paper.
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Yang, Y., Yang, Y., Yuwono, J.A. et al. High-entropy alloy nanowires for direct electrosynthesis of chlorine from seawater. Nat. Synth (2026). https://doi.org/10.1038/s44160-026-00999-5
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DOI: https://doi.org/10.1038/s44160-026-00999-5


