Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

Shirzadi, Erfan; Jin, Qiu; Zeraati, Ali Shayesteh; Dorakhan, Roham; Goncalves, Tiago J.; Abed, Jehad; Lee, Byoung-Hoon; Rasouli, Armin Sedighian; Wicks, Joshua; Zhang, Jinqiang; Ou, Pengfei; Boureau, Victor; Park, Sungjin; Ni, Weiyan; Lee, Geonhui; Tian, Cong; Meira, Debora Motta; Sinton, David; Siahrostami, Samira; Sargent, Edward H.

doi:10.1038/s41467-024-47319-z

Title: Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

Journal Article · 06 April 2024 · Nature Communications

DOI: https://doi.org/10.1038/s41467-024-47319-z · OSTI ID:2470192

^[1]; Jin, Qiu ^[2]; Zeraati, Ali Shayesteh ^[1];

^[1];

^[2];

^[1]; Lee, Byoung-Hoon ^[1]; Rasouli, Armin Sedighian ^[1];

^[1];

^[3]; Park, Sungjin ^[1];

^[1];

^[4];

^[1]; Siahrostami, Samira ^[5];

^[1]

Univ. of Toronto, ON (Canada)
Univ. of Calgary, AB (Canada)
Ecole Polytechnique Federale Lausanne (EPFL) (Switzerland)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Canadian Light Source Inc., Saskatoon, SK (Canada)
Simon Fraser Univ., Burnaby, BC (Canada)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Swiss National Science Foundation; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2470192

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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surface assembly

Title: Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

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