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Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction

Author

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  • Antonia Herzog

    (Fritz Haber Institute of the Max-Planck Society
    Research Laboratory of Electronics)

  • Mauricio Lopez Luna

    (Fritz Haber Institute of the Max-Planck Society
    Lawrence Berkeley National Laboratory)

  • Hyo Sang Jeon

    (Fritz Haber Institute of the Max-Planck Society
    Seongbuk-gu)

  • Clara Rettenmaier

    (Fritz Haber Institute of the Max-Planck Society)

  • Philipp Grosse

    (Fritz Haber Institute of the Max-Planck Society)

  • Arno Bergmann

    (Fritz Haber Institute of the Max-Planck Society)

  • Beatriz Roldan Cuenya

    (Fritz Haber Institute of the Max-Planck Society)

Abstract

Pulsed CO2 electroreduction (CO2RR) has recently emerged as a facile way to in situ tune the product selectivity, in particular toward ethanol, without re-designing the catalytic system. However, in-depth mechanistic understanding requires comprehensive operando time-resolved studies to identify the kinetics and dynamics of the electrocatalytic interface. Here, we track the adsorbates and the catalyst state of pre-reduced Cu2O nanocubes ( ~ 30 nm) during pulsed CO2RR using sub-second time-resolved operando Raman spectroscopy. By screening a variety of product-steering pulse length conditions, we unravel the critical role of co-adsorbed OH and CO on the Cu surface next to the oxidative formation of Cu-Oad or CuOx/(OH)y species, impacting the kinetics of CO adsorption and boosting the ethanol selectivity. However, a too low OHad coverage following the formation of bulk-like Cu2O induces a significant increase in the C1 selectivity, while a too high OHad coverage poisons the surface for C-C coupling. Thus, we unveil the importance of co-adsorbed OH on the alcohol formation under CO2RR conditions and thereby, pave the way for improved catalyst design and operating conditions.

Suggested Citation

  • Antonia Herzog & Mauricio Lopez Luna & Hyo Sang Jeon & Clara Rettenmaier & Philipp Grosse & Arno Bergmann & Beatriz Roldan Cuenya, 2024. "Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48052-3
    DOI: 10.1038/s41467-024-48052-3
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    References listed on IDEAS

    as
    1. Rosa M. Arán-Ais & Fabian Scholten & Sebastian Kunze & Rubén Rizo & Beatriz Roldan Cuenya, 2020. "The role of in situ generated morphological motifs and Cu(i) species in C2+ product selectivity during CO2 pulsed electroreduction," Nature Energy, Nature, vol. 5(4), pages 317-325, April.
    2. Yufei Cao & Zhu Chen & Peihao Li & Adnan Ozden & Pengfei Ou & Weiyan Ni & Jehad Abed & Erfan Shirzadi & Jinqiang Zhang & David Sinton & Jun Ge & Edward H. Sargent, 2023. "Surface hydroxide promotes CO2 electrolysis to ethylene in acidic conditions," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    3. Jing Li & Xiaoxia Chang & Haochen Zhang & Arnav S. Malkani & Mu-jeng Cheng & Bingjun Xu & Qi Lu, 2021. "Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper," Nature Communications, Nature, vol. 12(1), pages 1-11, December.
    4. Hemma Mistry & Ana Sofia Varela & Cecile S. Bonifacio & Ioannis Zegkinoglou & Ilya Sinev & Yong-Wook Choi & Kim Kisslinger & Eric A. Stach & Judith C. Yang & Peter Strasser & Beatriz Roldan Cuenya, 2016. "Correction: Corrigendum: Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene," Nature Communications, Nature, vol. 7(1), pages 1-1, December.
    5. Hemma Mistry & Ana Sofia Varela & Cecile S. Bonifacio & Ioannis Zegkinoglou & Ilya Sinev & Yong-Wook Choi & Kim Kisslinger & Eric A. Stach & Judith C. Yang & Peter Strasser & Beatriz Roldan Cuenya, 2016. "Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene," Nature Communications, Nature, vol. 7(1), pages 1-9, November.
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    Cited by:

    1. Ke Ye & Tian-Wen Jiang & Hyun Dong Jung & Peng Shen & So Min Jang & Zhe Weng & Seoin Back & Wen-Bin Cai & Kun Jiang, 2024. "Molecular level insights on the pulsed electrochemical CO2 reduction," Nature Communications, Nature, vol. 15(1), pages 1-12, December.

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