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Selective electrosynthesis of chlorine disinfectants from seawater

Nature Sustainability volume 7, pages 148–157 (2024)Cite this article

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Abstract

As one of the most widely used disinfectants, active chlorine is synthesized predominantly through electrolysis of saturated sodium chloride solutions, an industrial process known as the chlor-alkali process, with high energy consumption. Seawater is an abundant source of chloride and thus an ideal alternative electrolyte. However, substantial challenges are to be addressed, notably the competing oxygen evolution reaction and progressive anode passivation due to the presence of rich cations in seawater. Here, we show durable and efficient active chlorine electrosynthesis directly from natural seawater with intrinsic turnover frequency and mass activity two orders of magnitude higher than the state of the art. The essential chemistry is an Fe-doped Ti4O7 anode that strengthens the electrophilicity of lattice oxygen to allow for site-selective chloride activation at remarkably lowered kinetic overpotentials relative to the oxygen evolution reaction, while also impeding the precipitation of alkaline earth metal cations on the Ti4O7 surface. A seawater splitting device with an integrated commercial silicon photovoltaic cell delivers an impressive active chlorine production rate of 3.15 mg min−1 for effective simulated ballast water disinfection. This work suggests the possibility to substantially improve the sustainability of the chlor-alkali process without compromising the synthetic performance for the mass production of disinfectants.

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Fig. 1: Fine-structure characterizations.
Fig. 2: Electrochemical performance.
Fig. 3: Reaction mechanism study.
Fig. 4: Electrochemical stability.
Fig. 5: DFT calculations of CER and AC synthesis.
Fig. 6: Reactor design and performance.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (grant nos. 2022YFC3702101, 2021YFA1201701, 2022YFA1505000), the National Natural Science Foundation of China (grant nos. U22A20402, 21936003, 22076061, 22206124), the Natural Science Foundation of Shanghai (grant no. 23ZR1431000) and the China Postdoctoral Science Foundation (grant no. 2022M712049).

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Authors and Affiliations

  1. Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan, China

    Shengxi Zhao, Yaqian Jiang, Minzi Liao, Hongwei Sun & Lizhi Zhang

  2. School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, China

    Hao Li, Jie Dai, Guangming Zhan, Yanbiao Shi, Cancan Ling, Yancai Yao & Lizhi Zhang

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  1. Shengxi Zhao
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Contributions

L.Z. and H.L. supervised the project. H.L., S.Z. and H.S. conceived and designed the experiments. S.Z. conducted the material synthesis and characterizations, the electrochemical experiments and the DFT calculations. G.Z. contributed to the DFT calculations. H.S., Y.S. and Y.J. contributed to the sterilization experiment. M.L. and C.L. contributed to the electrode manufacture. J.D. and Y.Y. commented on the manuscript. S.Z., H.L. and L.Z. wrote the manuscript.

Corresponding authors

Correspondence to Hao Li, Hongwei Sun or Lizhi Zhang.

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The authors declare no competing interests.

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Nature Sustainability thanks Kai Exner and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–37 and Tables 1–3.

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Source data

Source Data Fig. 1

Source data for the XRD patterns, normalized XANES spectra and Fourier-transform K-edge EXAFS spectra.

Source Data Fig. 2

Source data for the electrochemical performance.

Source Data Fig. 3

Source data of electrochemically active surface areas, Cl 2p XPS and H2-TPR.

Source Data Fig. 4

Source data for the chronopotentiometric curve, Ca2+ 2p XPS and Zeta potential.

Source Data Fig. 5

Source data for TDOS and PDOS.

Source Data Fig. 6

Source data for the J-V curve, AC electrochemical synthesis and sterilization.

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Zhao, S., Li, H., Dai, J. et al. Selective electrosynthesis of chlorine disinfectants from seawater. Nat Sustain 7, 148–157 (2024). https://doi.org/10.1038/s41893-023-01265-8

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