IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v15y2024i1d10.1038_s41467-024-48052-3.html
   My bibliography  Save this article

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

Author

Listed:
  • 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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-024-48052-3
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-024-48052-3?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    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. 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.
    3. 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.
    4. 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.
    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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Wei Liu & Pengbo Zhai & Aowen Li & Bo Wei & Kunpeng Si & Yi Wei & Xingguo Wang & Guangda Zhu & Qian Chen & Xiaokang Gu & Ruifeng Zhang & Wu Zhou & Yongji Gong, 2022. "Electrochemical CO2 reduction to ethylene by ultrathin CuO nanoplate arrays," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    2. Lei Wang & Zhiwen Chen & Yi Xiao & Linke Huang & Xiyang Wang & Holly Fruehwald & Dmitry Akhmetzyanov & Mathew Hanson & Zuolong Chen & Ning Chen & Brant Billinghurst & Rodney D. L. Smith & Chandra Veer, 2024. "Stabilized Cuδ+-OH species on in situ reconstructed Cu nanoparticles for CO2-to-C2H4 conversion in neutral media," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    3. Shijia Mu & Honglei Lu & Qianbao Wu & Lei Li & Ruijuan Zhao & Chang Long & Chunhua Cui, 2022. "Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    4. Erfan Shirzadi & Qiu Jin & Ali Shayesteh Zeraati & Roham Dorakhan & Tiago J. Goncalves & Jehad Abed & Byoung-Hoon Lee & Armin Sedighian Rasouli & Joshua Wicks & Jinqiang Zhang & Pengfei Ou & Victor Bo, 2024. "Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    5. Yajun Zheng & Hedan Yao & Ruinan Di & Zhicheng Xiang & Qiang Wang & Fangfang Lu & Yu Li & Guangxing Yang & Qiang Ma & Zhiping Zhang, 2022. "Water coordinated on Cu(I)-based catalysts is the oxygen source in CO2 reduction to CO," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    6. Xiaozhi Su & Zhuoli Jiang & Jing Zhou & Hengjie Liu & Danni Zhou & Huishan Shang & Xingming Ni & Zheng Peng & Fan Yang & Wenxing Chen & Zeming Qi & Dingsheng Wang & Yu Wang, 2022. "Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    7. Qiong Lei & Liang Huang & Jun Yin & Bambar Davaasuren & Youyou Yuan & Xinglong Dong & Zhi-Peng Wu & Xiaoqian Wang & Ke Xin Yao & Xu Lu & Yu Han, 2022. "Structural evolution and strain generation of derived-Cu catalysts during CO2 electroreduction," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    8. Ahmad, Naveed & Chen, Ying & Wang, Xiaoxiao & Sun, Peixu & Bao, Yuting & Xu, Xia, 2022. "Highly efficient electrochemical upgrade of CO2 to CO using AMP capture solution as electrolyte," Renewable Energy, Elsevier, vol. 189(C), pages 444-453.
    9. Ruiz-López, Estela & Gandara-Loe, Jesús & Baena-Moreno, Francisco & Reina, Tomas Ramirez & Odriozola, José Antonio, 2022. "Electrocatalytic CO2 conversion to C2 products: Catalysts design, market perspectives and techno-economic aspects," Renewable and Sustainable Energy Reviews, Elsevier, vol. 161(C).
    10. Chia-Shuo Hsu & Jiali Wang & You-Chiuan Chu & Jui-Hsien Chen & Chia-Ying Chien & Kuo-Hsin Lin & Li Duan Tsai & Hsiao-Chien Chen & Yen-Fa Liao & Nozomu Hiraoka & Yuan-Chung Cheng & Hao Ming Chen, 2023. "Activating dynamic atomic-configuration for single-site electrocatalyst in electrochemical CO2 reduction," Nature Communications, Nature, vol. 14(1), pages 1-14, December.
    11. Yong Yin & Bingcheng Luo & Kezhi Li & Benjamin M. Moskowitz & Bar Mosevitzky Lis & Israel E. Wachs & Minghui Zhu & Ye Sun & Tianle Zhu & Xiang Li, 2024. "Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NOx," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    12. Zhiwen Jiang & Carine Clavaguéra & Changjiang Hu & Sergey A. Denisov & Shuning Shen & Feng Hu & Jun Ma & Mehran Mostafavi, 2023. "Direct time-resolved observation of surface-bound carbon dioxide radical anions on metallic nanocatalysts," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    13. Wenpeng Ni & Houjun Chen & Naizhuo Tang & Ting Hu & Wei Zhang & Yan Zhang & Shiguo Zhang, 2024. "High-purity ethylene production via indirect carbon dioxide electrochemical reduction," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    14. Marvin L. Frisch & Longfei Wu & Clément Atlan & Zhe Ren & Madeleine Han & Rémi Tucoulou & Liang Liang & Jiasheng Lu & An Guo & Hong Nhan Nong & Aleks Arinchtein & Michael Sprung & Julie Villanova & Ma, 2023. "Unraveling the synergistic effects of Cu-Ag tandem catalysts during electrochemical CO2 reduction using nanofocused X-ray probes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    15. Meng He & Yongmeng Wu & Rui Li & Yuting Wang & Cuibo Liu & Bin Zhang, 2023. "Aqueous pulsed electrochemistry promotes C−N bond formation via a one-pot cascade approach," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    16. Seung-Jae Shin & Hansol Choi & Stefan Ringe & Da Hye Won & Hyung-Suk Oh & Dong Hyun Kim & Taemin Lee & Dae-Hyun Nam & Hyungjun Kim & Chang Hyuck Choi, 2022. "A unifying mechanism for cation effect modulating C1 and C2 productions from CO2 electroreduction," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    17. Mengran Li & Erdem Irtem & Hugo-Pieter Iglesias van Montfort & Maryam Abdinejad & Thomas Burdyny, 2022. "Energy comparison of sequential and integrated CO2 capture and electrochemical conversion," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    18. Yanmei Huang & Caihong He & Chuanqi Cheng & Shuhe Han & Meng He & Yuting Wang & Nannan Meng & Bin Zhang & Qipeng Lu & Yifu Yu, 2023. "Pulsed electroreduction of low-concentration nitrate to ammonia," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    19. Zhang, Xuewei & Zhou, Wei & Huang, Yuming & Ding, Yani & Li, Junfeng & Xie, Liang & Yu, Yang & Chen, Jiaxiang & Sun, Miaoting & Meng, Xiaoxiao, 2024. "Enhanced hydrogen production enabled by pulsed potential coupled sulfite electrooxidation water electrolysis system," Renewable Energy, Elsevier, vol. 227(C).
    20. Jeongjin Kim & Youngseok Yu & Tae Won Go & Jean-Jacques Gallet & Fabrice Bournel & Bongjin Simon Mun & Jeong Young Park, 2023. "Revealing CO2 dissociation pathways at vicinal copper (997) interfaces," Nature Communications, Nature, vol. 14(1), pages 1-10, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48052-3. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.