Highly Selective Active Chlorine Generation Electrocatalyzed by Co3O4 Nanoparticles: Mechanistic Investigation through in Situ Electrokinetic and Spectroscopic Analyses

  • Heonjin Ha
    Heonjin Ha
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
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  • Kyoungsuk Jin
    Kyoungsuk Jin
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
  • Sunghak Park
    Sunghak Park
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    More by Sunghak Park
  • Kang-Gyu Lee
    Kang-Gyu Lee
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    More by Kang-Gyu Lee
  • Kang Hee Cho
    Kang Hee Cho
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    More by Kang Hee Cho
  • Hongmin Seo
    Hongmin Seo
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    More by Hongmin Seo
  • Hyo-Yong Ahn
    Hyo-Yong Ahn
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    More by Hyo-Yong Ahn
  • Yoon Ho Lee
    Yoon Ho Lee
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
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  • , and 
  • Ki Tae Nam*
    Ki Tae Nam
    Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Korea
    *E-mail: [email protected]
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Cite this: J. Phys. Chem. Lett. 2019, 10, 6, 1226–1233
Publication Date (Web):February 28, 2019
https://doi.org/10.1021/acs.jpclett.9b00547
Copyright © 2019 American Chemical Society
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Abstract

The reaction mechanism of electrochemical chloride oxidation at neutral pH is different from that at acidic pH, in which a commercial chlor-alkali process has been developed. Different proton concentrations and accelerated hydrolysis of the generated chlorine into hypochlorous acid at high pH can change the electrokinetics and stability of reaction intermediates. We have investigated a unique reaction mechanism of Co3O4 nanoparticles for chloride oxidation at neutral pH. In contrast with water oxidation, the valency of cobalt was not changed during chloride oxidation. Interestingly, a new intermediate of Co–Cl was captured spectroscopically, distinct from the reaction intermediate at acidic pH. In addition, Co3O4 nanoparticles exhibited high selectivity for active chlorine generation at neutral pH, comparable to commercially available RuO2-based catalysts. We believe that this study provides insight into designing efficient electrocatalysts for active chlorine generation at neutral pH, which can be practically applied to electrochemical water treatment coupled to hydrogen production.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.9b00547.

  • Detailed experimental methods, structural characterization, Figures S1–S12, Scheme S1, and Table S1 (PDF)

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