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; Edward H. Sargent

doi:10.1038/s41467-024-47319-z

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^*, Edward H. Sargent^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

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.

Original language	English (US)
Article number	2995
Journal	Nature communications
Volume	15
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-47319-z
State	Published - Dec 2024

Funding

This work was supported by the Swiss National Science Foundation (SNSF P2ELP2_199812, E.S. and P500PN_214309, E.S.) and Natural Sciences and Engineering Research Council of Canada (NSERC). This research used resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, E.H.S and the Canadian Light Source (CLS) and its funding partners. Q.J., and\u00A0T.J.G. acknowledge the support from the University of Calgary\u2032s Canada First Research Excellence Fund Program, the Global Research Initiative in Sustainable Low Carbon Unconventional Resources. S.S. acknowledges\u00A0the support from Natural Sciences and Engineering Research Council (NSERC) of Canada (Discovery Grant No. RGPIN-2023-05298).\u00A0The computational research was enabled in part by support provided by computational resource at the University of Calgary (www.rcs.ucalgary.ca) and Compute Canada (www.computecanada.ca). The authors thank D.M.M. and Dr. Zou Finfrock from 20BM beamline at APS, and Dr. Mohsen Shakouri, Dr. Qunfeng Xiao, and Dr. Alisa Paterson from SXRMB at CLS and Dr. Tom Regier and Dr. James Dynes from SGM at CLS for assistance in collecting the X-ray absorption spectroscopy data. This work was supported by the Swiss National Science Foundation (SNSF P2ELP2_199812, E.S. and P500PN_214309, E.S.) and Natural Sciences and Engineering Research Council of Canada (NSERC). This research used resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, E.H.S and the Canadian Light Source (CLS) and its funding partners. Q.J., and T.J.G. acknowledge the support from the University of Calgary\u2032s Canada First Research Excellence Fund Program, the Global Research Initiative in Sustainable Low Carbon Unconventional Resources. S.S. acknowledges the support from Natural Sciences and Engineering Research Council (NSERC) of Canada (Discovery Grant No. RGPIN-2023-05298). The computational research was enabled in part by support provided by computational resource at the University of Calgary ( www.rcs.ucalgary.ca ) and Compute Canada ( www.computecanada.ca ). The authors thank D.M.M. and Dr. Zou Finfrock from 20BM beamline at APS, and Dr. Mohsen Shakouri, Dr. Qunfeng Xiao, and Dr. Alisa Paterson from SXRMB at CLS and Dr. Tom Regier and Dr. James Dynes from SGM at CLS for assistance in collecting the X-ray absorption spectroscopy data.

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

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Shirzadi, E., Jin, Q., Zeraati, A. S., Dorakhan, R., Goncalves, T. J., Abed, J., Lee, B. H., Rasouli, A. S., Wicks, J., Zhang, J., Ou, P., Boureau, V., Park, S., Ni, W., Lee, G., Tian, C., Meira, D. M., Sinton, D., Siahrostami, S., & Sargent, E. H. (2024). Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity. Nature communications, 15(1), Article 2995. https://doi.org/10.1038/s41467-024-47319-z

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title = "Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity",

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.",

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

note = "Publisher Copyright: {\textcopyright} The Author(s) 2024.",

year = "2024",

month = dec,

doi = "10.1038/s41467-024-47319-z",

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Shirzadi, E, Jin, Q, Zeraati, AS, Dorakhan, R, Goncalves, TJ, Abed, J, Lee, BH, Rasouli, AS, Wicks, J, Zhang, J, Ou, P, Boureau, V, Park, S, Ni, W, Lee, G, Tian, C, Meira, DM, Sinton, D, Siahrostami, S & Sargent, EH 2024, 'Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity', Nature communications, vol. 15, no. 1, 2995. https://doi.org/10.1038/s41467-024-47319-z

TY - JOUR

T1 - Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

AU - Shirzadi, Erfan

AU - Jin, Qiu

AU - Zeraati, Ali Shayesteh

AU - Dorakhan, Roham

AU - Goncalves, Tiago J.

AU - Abed, Jehad

AU - Lee, Byoung Hoon

AU - Rasouli, Armin Sedighian

AU - Wicks, Joshua

AU - Zhang, Jinqiang

AU - Ou, Pengfei

AU - Boureau, Victor

AU - Park, Sungjin

AU - Ni, Weiyan

AU - Lee, Geonhui

AU - Tian, Cong

AU - Meira, Debora Motta

AU - Sinton, David

AU - Siahrostami, Samira

AU - Sargent, Edward H.

PY - 2024/12

Y1 - 2024/12

N2 - 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.

AB - 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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VL - 15

JO - Nature communications

JF - Nature communications

IS - 1

M1 - 2995

ER -

Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

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