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

Wang, Jianchun and Cheng, Tao and Fenwick, Aidan Q. and Baroud, Turki N. and Rosas-Hernández, Alonso and Ko, Jeong Hoon and Gan, Quan and Goddard III, William A. and Grubbs, Robert H. (2021) Selective CO₂ Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface. Journal of the American Chemical Society, 143 (7). pp. 2857-2865. ISSN 0002-7863. doi:10.1021/jacs.0c12478.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription
Wang, Jianchun0000-0002-3998-8699
Cheng, Tao0000-0003-4830-177X
Fenwick, Aidan Q.0000-0003-4442-0878
Baroud, Turki N.0000-0001-6430-9128
Rosas-Hernández, Alonso0000-0002-0812-5591
Ko, Jeong Hoon0000-0003-2000-3789
Gan, Quan0000-0001-5908-4163
Goddard III, William A.0000-0003-0097-5716
Grubbs, Robert H.0000-0002-0057-7817
Alternate Title:Selective CO2 Electrochemical Reduction Enabled by a Tricomponent Copolymer Modifier on a Copper Surface
Additional Information:© 2021 American Chemical Society. Received: November 30, 2020; Published: February 11, 2021. This research benefited from the use of instrumentation made available by the Caltech CCE Multiuser Mass Spectrometry Laboratory. XPS data were collected at the Molecular Materials Research Center in the Beckman Institute of the California Institute of Technology. Nick Watkins is thanked for assistance with SEM experiments. Dr. Shunsuke Sato, Dr. Brendon J. McNicholas, and Dr. Yan Xu are thanked for their discussions. This study was supported by the King Fahd University of Petroleum and Minerals (R.H.G.) and the Joint Center for Artificial Photosynthesis, a Department of Energy (DOE) Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. The authors declare no competing financial interest.
Funding AgencyGrant Number
King Fahd University of Petroleum and Minerals (KFUPM)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Subject Keywords:Electrocatalysis, Selectivity, Electrodes, Polymers, Copolymers
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Issue or Number:7
Record Number:CaltechAUTHORS:20210216-080252695
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Official Citation: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, and Robert H. Grubbs. Journal of the American Chemical Society 2021 143 (7), 2857-2865; DOI: 10.1021/jacs.0c12478
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108057
Deposited By: Tony Diaz
Deposited On:16 Feb 2021 18:07
Last Modified:16 Nov 2021 19:08

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