Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

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 Boureau, Sungjin Park, Weiyan Ni, Geonhui Lee, Cong Tian, Debora Motta Meira, David Sinton, Samira Siahrostami () and Edward H. Sargent ()
Additional contact information
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
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
David Sinton: University of Toronto
Samira Siahrostami: Simon Fraser University
Edward H. Sargent: University of Toronto

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-47319-z

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