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Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst

Author

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  • Jie-Wei Chen

    (Southern University of Science and Technology
    Southern University of Science and Technology)

  • Zisheng Zhang

    (Southern University of Science and Technology
    Southern University of Science and Technology
    University of California, Los Angeles)

  • Hui-Min Yan

    (Southern University of Science and Technology
    Southern University of Science and Technology)

  • Guang-Jie Xia

    (Southern University of Science and Technology
    Southern University of Science and Technology)

  • Hao Cao

    (Southern University of Science and Technology
    Southern University of Science and Technology)

  • Yang-Gang Wang

    (Southern University of Science and Technology
    Southern University of Science and Technology)

Abstract

Fundamental understanding of the dynamic behaviors at the electrochemical interface is crucial for electrocatalyst design and optimization. Here, we revisit the oxygen reduction reaction mechanism on a series of transition metal (M = Fe, Co, Ni, Cu) single atom sites embedded in N-doped nanocarbon by ab initio molecular dynamics simulations with explicit solvation. We have identified the dissociative pathways and the thereby emerged solvated hydroxide species for all the proton-coupled electron transfer (PCET) steps at the electrochemical interface. Such hydroxide species can be dynamically confined in a “pseudo-adsorption” state at a few water layers away from the active site and respond to the redox event at the catalytic center in a coupled manner within timescale less than 1 ps. In the PCET steps, the proton species (in form of hydronium in neutral/acidic media or water in alkaline medium) can protonate the pseudo-adsorbed hydroxide without needing to travel to the direct catalyst surface. This, therefore, expands the reactive region beyond the direct catalyst surface, boosting the reaction kinetics via alleviating mass transfer limits. Our work implies that in catalysis the reaction species may not necessarily bind to the catalyst surface but be confined in an active region.

Suggested Citation

  • Jie-Wei Chen & Zisheng Zhang & Hui-Min Yan & Guang-Jie Xia & Hao Cao & Yang-Gang Wang, 2022. "Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-29357-7
    DOI: 10.1038/s41467-022-29357-7
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    1. Xiao Zhang & Yang Wang & Meng Gu & Maoyu Wang & Zisheng Zhang & Weiying Pan & Zhan Jiang & Hongzhi Zheng & Marcos Lucero & Hailiang Wang & George E. Sterbinsky & Qing Ma & Yang-Gang Wang & Zhenxing Fe, 2020. "Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction," Nature Energy, Nature, vol. 5(9), pages 684-692, September.
    2. Xing Zhang & Zishan Wu & Xiao Zhang & Liewu Li & Yanyan Li & Haomin Xu & Xiaoxiao Li & Xiaolu Yu & Zisheng Zhang & Yongye Liang & Hailiang Wang, 2017. "Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures," Nature Communications, Nature, vol. 8(1), pages 1-8, April.
    3. Daniel Malko & Anthony Kucernak & Thiago Lopes, 2016. "In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts," Nature Communications, Nature, vol. 7(1), pages 1-7, December.
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    Cited by:

    1. Zhihe Liu & Hua Tan & Bo Li & Zehua Hu & De-en Jiang & Qiaofeng Yao & Lei Wang & Jianping Xie, 2023. "Ligand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    2. Peng Li & Yuzhou Jiao & Yaner Ruan & Houguo Fei & Yana Men & Cunlan Guo & Yuen Wu & Shengli Chen, 2023. "Revealing the role of double-layer microenvironments in pH-dependent oxygen reduction activity over metal-nitrogen-carbon catalysts," Nature Communications, Nature, vol. 14(1), pages 1-12, December.

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