Selective CO2 Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface

Jianchun Wang; Tao Cheng; Aidan Q. Fenwick; Turki N. Baroud; Alonso Rosas-Hernández; Jeong Hoon Ko; Quan Gan; William A. Goddard III; Robert H. Grubbs

doi:10.1021/jacs.0c12478

Selective CO₂ Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface

Jianchun Wang, Tao Cheng, Aidan Q. Fenwick, Turki N. Baroud, Alonso Rosas-Hernández, Jeong Hoon Ko, Quan Gan, William A. Goddard III^*, Robert H. Grubbs^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

135 Citations (Scopus)

Abstract

Electrochemical CO₂ reduction over Cu could provide value-added multicarbon hydrocarbons and alcohols. Despite recent breakthroughs, it remains a significant challenge to design a catalytic system with high product selectivity. Here we demonstrate that a high selectivity of ethylene (55%) and C₂₊ products (77%) could be achieved by a highly modular tricomponent copolymer modified Cu electrode, rivaling the best performance using other modified polycrystalline Cu foil catalysts. Such a copolymer can be conveniently prepared by a ring-opening metathesis polymerization, thereby offering a new degree of freedom for tuning the selectivity. Control experiments indicate all three components are essential for the selectivity enhancement. A surface characterization showed that the incorporation of a phenylpyridinium component increased the film robustness against delamination. It was also shown that its superior performance is not due to a morphology change of the Cu underneath. Molecular dynamics (MD) simulations indicate that a combination of increased local CO₂ concentration, increased porosity for gas diffusion, and the local electric field effect together contribute to the increased ethylene and C₂₊ product selectivity.

Original language	English
Journal	Journal of the American Chemical Society
Volume	143
Issue	7
Pages (from-to)	2857-2865
Number of pages	9
ISSN	0002-7863
DOIs	https://doi.org/10.1021/jacs.0c12478
Publication status	Published - Feb 2021
Externally published	Yes

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title = "Selective CO2 Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface",

abstract = "Electrochemical CO2 reduction over Cu could provide value-added multicarbon hydrocarbons and alcohols. Despite recent breakthroughs, it remains a significant challenge to design a catalytic system with high product selectivity. Here we demonstrate that a high selectivity of ethylene (55%) and C2+ products (77%) could be achieved by a highly modular tricomponent copolymer modified Cu electrode, rivaling the best performance using other modified polycrystalline Cu foil catalysts. Such a copolymer can be conveniently prepared by a ring-opening metathesis polymerization, thereby offering a new degree of freedom for tuning the selectivity. Control experiments indicate all three components are essential for the selectivity enhancement. A surface characterization showed that the incorporation of a phenylpyridinium component increased the film robustness against delamination. It was also shown that its superior performance is not due to a morphology change of the Cu underneath. Molecular dynamics (MD) simulations indicate that a combination of increased local CO2 concentration, increased porosity for gas diffusion, and the local electric field effect together contribute to the increased ethylene and C2+ product selectivity.",

author = "Jianchun Wang and Tao Cheng and Fenwick, {Aidan Q.} and Baroud, {Turki N.} and Alonso Rosas-Hern{\'a}ndez and Ko, {Jeong Hoon} and Quan Gan and {Goddard III}, {William A.} and Grubbs, {Robert H.}",

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doi = "10.1021/jacs.0c12478",

language = "English",

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Selective CO₂ Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface. / Wang, Jianchun; Cheng, Tao; Fenwick, Aidan Q. et al.
In: Journal of the American Chemical Society, Vol. 143, No. 7, 02.2021, p. 2857-2865.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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AU - Wang, Jianchun

AU - Cheng, Tao

AU - Fenwick, Aidan Q.

AU - Baroud, Turki N.

AU - Rosas-Hernández, Alonso

AU - Ko, Jeong Hoon

AU - Gan, Quan

AU - Goddard III, William A.

AU - Grubbs, Robert H.

PY - 2021/2

Y1 - 2021/2

N2 - Electrochemical CO2 reduction over Cu could provide value-added multicarbon hydrocarbons and alcohols. Despite recent breakthroughs, it remains a significant challenge to design a catalytic system with high product selectivity. Here we demonstrate that a high selectivity of ethylene (55%) and C2+ products (77%) could be achieved by a highly modular tricomponent copolymer modified Cu electrode, rivaling the best performance using other modified polycrystalline Cu foil catalysts. Such a copolymer can be conveniently prepared by a ring-opening metathesis polymerization, thereby offering a new degree of freedom for tuning the selectivity. Control experiments indicate all three components are essential for the selectivity enhancement. A surface characterization showed that the incorporation of a phenylpyridinium component increased the film robustness against delamination. It was also shown that its superior performance is not due to a morphology change of the Cu underneath. Molecular dynamics (MD) simulations indicate that a combination of increased local CO2 concentration, increased porosity for gas diffusion, and the local electric field effect together contribute to the increased ethylene and C2+ product selectivity.

AB - Electrochemical CO2 reduction over Cu could provide value-added multicarbon hydrocarbons and alcohols. Despite recent breakthroughs, it remains a significant challenge to design a catalytic system with high product selectivity. Here we demonstrate that a high selectivity of ethylene (55%) and C2+ products (77%) could be achieved by a highly modular tricomponent copolymer modified Cu electrode, rivaling the best performance using other modified polycrystalline Cu foil catalysts. Such a copolymer can be conveniently prepared by a ring-opening metathesis polymerization, thereby offering a new degree of freedom for tuning the selectivity. Control experiments indicate all three components are essential for the selectivity enhancement. A surface characterization showed that the incorporation of a phenylpyridinium component increased the film robustness against delamination. It was also shown that its superior performance is not due to a morphology change of the Cu underneath. Molecular dynamics (MD) simulations indicate that a combination of increased local CO2 concentration, increased porosity for gas diffusion, and the local electric field effect together contribute to the increased ethylene and C2+ product selectivity.

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Selective CO₂ Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface

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