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Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction

Author

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  • Shijia Mu

    (University of Electronic Science and Technology of China)

  • Honglei Lu

    (University of Electronic Science and Technology of China)

  • Qianbao Wu

    (University of Electronic Science and Technology of China)

  • Lei Li

    (University of Electronic Science and Technology of China)

  • Ruijuan Zhao

    (University of Electronic Science and Technology of China)

  • Chang Long

    (University of Electronic Science and Technology of China)

  • Chunhua Cui

    (University of Electronic Science and Technology of China)

Abstract

Cuδ+ sites on the surface of oxide-derived copper (OD-Cu) are of vital importance in electrochemical CO2 reduction reaction (CO2RR). However, the underlying reason for the dynamically existing Cuδ+ species, although thermodynamically unstable under reductive CO2RR conditions, remains uncovered. Here, by using electron paramagnetic resonance, we identify the highly oxidative hydroxyl radicals (OH•) formed at room temperature in HCO3- solutions. In combination with in situ Raman spectroscopy, secondary ion mass spectrometry, and isotope-labelling, we demonstrate a dynamic reduction/reoxidation behavior at the surface of OD-Cu and reveal that the fast oxygen exchange between HCO3- and H2O provides oxygen sources for the formation of OH• radicals. In addition, their continuous generations can cause spontaneous oxidation of Cu electrodes and produce surface CuOx species. Significantly, this work suggests that there is a “seesaw-effect” between the cathodic reduction and the OH•-induced reoxidation, determining the chemical state and content of Cuδ+ species in CO2RR. This insight is supposed to thrust an understanding of the crucial role of electrolytes in CO2RR.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31498-8
    DOI: 10.1038/s41467-022-31498-8
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    References listed on IDEAS

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    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. 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.
    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. "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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    1. Huizhen Zhang & Pengfei Sun & Xiaozhen Fei & Xuejiao Wu & Zongyi Huang & Wanfu Zhong & Qiaobin Gong & Yanping Zheng & Qinghong Zhang & Shunji Xie & Gang Fu & Ye Wang, 2024. "Unusual facet and co-catalyst effects in TiO2-based photocatalytic coupling of methane," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Xin Chen & Junxiang Chen & Huayu Chen & Qiqi Zhang & Jiaxuan Li & Jiwei Cui & Yanhui Sun & Defa Wang & Jinhua Ye & Lequan Liu, 2023. "Promoting water dissociation for efficient solar driven CO2 electroreduction via improving hydroxyl adsorption," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    3. 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.

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