Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper

Hongyu An; Longfei Wu; Laurens D B Mandemaker; Shuang Yang; Jim de Ruiter; Jochem H J Wijten; Joris C L Janssens; Thomas Hartman; Ward van der Stam; Bert M Weckhuysen

doi:10.1002/anie.202104114

Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper

Hongyu An, Longfei Wu, Laurens D B Mandemaker, Shuang Yang, Jim de Ruiter, Jochem H J Wijten, Joris C L Janssens, Thomas Hartman, Ward van der Stam, Bert M Weckhuysen

Sub Inorganic Chemistry and Catalysis

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

Abstract

The electrocatalytic carbon dioxide (CO₂) reduction reaction (CO₂RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO₂RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below −0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO₂RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm⁻¹, is related to C−C coupling and ethylene production (−0.9 V vs. RHE), whereas lower cathodic bias (−0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm⁻¹.

Original language	English
Pages (from-to)	16576-16584
Number of pages	9
Journal	Angewandte Chemie-International Edition
Volume	60
Issue number	30
Early online date	14 Apr 2021
DOIs	https://doi.org/10.1002/anie.202104114
Publication status	Published - 19 Jul 2021

Bibliographical note

Funding Information:
This work was supported by the Strategic Alliance between Utrecht University, University Medical Center Utrecht and Technical University Eindhoven. B.M.W. acknowledges funding from the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We would like to thank all the students and staff who have strived to keep our lab running in this special period of our lives.

Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Keywords

Raman spectroscopy
copper
electrocatalysis
in situ

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An, H., Wu, L., Mandemaker, L. D. B., Yang, S., de Ruiter, J., Wijten, J. H. J., Janssens, J. C. L., Hartman, T., van der Stam, W., & Weckhuysen, B. M. (2021). Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper. Angewandte Chemie-International Edition, 60(30), 16576-16584. https://doi.org/10.1002/anie.202104114

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title = "Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper",

abstract = "The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO2RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below −0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO2RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm−1, is related to C−C coupling and ethylene production (−0.9 V vs. RHE), whereas lower cathodic bias (−0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm−1.",

keywords = "Raman spectroscopy, copper, electrocatalysis, in situ",

author = "Hongyu An and Longfei Wu and Mandemaker, {Laurens D B} and Shuang Yang and {de Ruiter}, Jim and Wijten, {Jochem H J} and Janssens, {Joris C L} and Thomas Hartman and {van der Stam}, Ward and Weckhuysen, {Bert M}",

note = "Funding Information: This work was supported by the Strategic Alliance between Utrecht University, University Medical Center Utrecht and Technical University Eindhoven. B.M.W. acknowledges funding from the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We would like to thank all the students and staff who have strived to keep our lab running in this special period of our lives. Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

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An, H, Wu, L, Mandemaker, LDB, Yang, S, de Ruiter, J, Wijten, JHJ, Janssens, JCL , Hartman, T , van der Stam, W & Weckhuysen, BM 2021, 'Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper', Angewandte Chemie-International Edition, vol. 60, no. 30, pp. 16576-16584. https://doi.org/10.1002/anie.202104114

Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper. / An, Hongyu; Wu, Longfei; Mandemaker, Laurens D B et al.
In: Angewandte Chemie-International Edition, Vol. 60, No. 30, 19.07.2021, p. 16576-16584.

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

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AU - An, Hongyu

AU - Wu, Longfei

AU - Mandemaker, Laurens D B

AU - Yang, Shuang

AU - de Ruiter, Jim

AU - Wijten, Jochem H J

AU - Janssens, Joris C L

AU - Hartman, Thomas

AU - van der Stam, Ward

AU - Weckhuysen, Bert M

N1 - Funding Information: This work was supported by the Strategic Alliance between Utrecht University, University Medical Center Utrecht and Technical University Eindhoven. B.M.W. acknowledges funding from the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We would like to thank all the students and staff who have strived to keep our lab running in this special period of our lives. Publisher Copyright: © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

PY - 2021/7/19

Y1 - 2021/7/19

N2 - The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO2RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below −0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO2RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm−1, is related to C−C coupling and ethylene production (−0.9 V vs. RHE), whereas lower cathodic bias (−0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm−1.

AB - The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO2RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below −0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO2RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm−1, is related to C−C coupling and ethylene production (−0.9 V vs. RHE), whereas lower cathodic bias (−0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm−1.

KW - Raman spectroscopy

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KW - electrocatalysis

KW - in situ

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ER -

Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper

Abstract

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Keywords

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