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Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

Author

Listed:
  • Erfan Shirzadi

    (University of Toronto)

  • Qiu Jin

    (University of Calgary)

  • Ali Shayesteh Zeraati

    (University of Toronto)

  • Roham Dorakhan

    (University of Toronto)

  • Tiago J. Goncalves

    (University of Calgary)

  • Jehad Abed

    (University of Toronto
    University of Toronto)

  • Byoung-Hoon Lee

    (University of Toronto)

  • Armin Sedighian Rasouli

    (University of Toronto)

  • Joshua Wicks

    (University of Toronto)

  • Jinqiang Zhang

    (University of Toronto)

  • Pengfei Ou

    (University of Toronto)

  • Victor Boureau

    (École Polytechnique Fédérale de Lausanne (EPFL))

  • Sungjin Park

    (University of Toronto)

  • Weiyan Ni

    (University of Toronto)

  • Geonhui Lee

    (University of Toronto)

  • Cong Tian

    (University of Toronto)

  • Debora Motta Meira

    (Argonne National Laboratory
    Canadian Light Source Inc.)

  • David Sinton

    (University of Toronto)

  • Samira Siahrostami

    (Simon Fraser University)

  • Edward H. Sargent

    (University of Toronto)

Abstract

Improving the kinetics and selectivity of CO2/CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp2 hybridization of CO(ad), facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC–CH2)* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C–O, Cu–C, and C–S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47319-z
    DOI: 10.1038/s41467-024-47319-z
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    References listed on IDEAS

    as
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