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Probing Cation Effects on *CO Intermediates from Electroreduction of CO2 through Operando Raman Spectroscopy
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    Probing Cation Effects on *CO Intermediates from Electroreduction of CO2 through Operando Raman Spectroscopy
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    • Si Young Lee
      Si Young Lee
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea
      More by Si Young Lee
    • Jimin Kim
      Jimin Kim
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea
      More by Jimin Kim
    • Gwangsu Bak
      Gwangsu Bak
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      More by Gwangsu Bak
    • Eunchong Lee
      Eunchong Lee
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      More by Eunchong Lee
    • Dayeon Kim
      Dayeon Kim
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      More by Dayeon Kim
    • Suhwan Yoo
      Suhwan Yoo
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      More by Suhwan Yoo
    • Jiwon Kim
      Jiwon Kim
      Department of Chemical and Biomolecular Engineering, Yonsei-KIST Convergence Research Institute, Yonsei University, Seoul 03722, Republic of Korea
      Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
      More by Jiwon Kim
    • Hyewon Yun
      Hyewon Yun
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea
      More by Hyewon Yun
    • Yun Jeong Hwang*
      Yun Jeong Hwang
      Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Republic of Korea
      Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea
      *Email: [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 42, 23068–23075
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    https://doi.org/10.1021/jacs.3c05799
    Published October 9, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    Cations in an electrolyte modulate microenvironments near the catalyst surface and affect product distribution from an electrochemical CO2 reduction reaction, and thus, their interaction with intermediate states has been tried to be probed. Herein, we directly observed the cation effect on *CO intermediates on the Cu(OH)2-derived catalyst in real time through operando surface-enhanced Raman spectroscopy at high overpotentials (−1.0 VRHE). Atop *CO peaks are composed of low-frequency binding *CO (*COLFB) and high-frequency binding *CO (*COHFB) because of their adsorption sites. These two *CO intermediates are found to have different sensitivities to the cation-induced field, and each *CO is proposed to be suitably stabilized for efficient C–C coupling. The proportions between *COHFB and *COLFB are dependent on the type of alkali cations, and the increases in the *COHFB ratio have a high correlation with selective C2H4 production under K+ and Cs+, indicating that *COHFB is the dominant and fast active species. In addition, as the hydrated cation size decreases, *COLFB is more sensitively red-shifted than *COHFB, which promotes C–C coupling and suppresses C1 products. Through time-resolved operando measurements, dynamic changes between the two *CO species are observed, showing the rapid initial adsorption of *COHFB and subsequently reaching a steady ratio between *COLFB and *COHFB.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c05799.

    • Detailed experimental section, X-ray absorption spectroscopy characterization, flow cell experiment, additional SEM images, operando Raman full spectrum, detailed deconvolution information, and the additional 3D operando Raman spectrum plot (PDF)

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 42, 23068–23075
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c05799
    Published October 9, 2023
    Copyright © 2023 American Chemical Society

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