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Published February 24, 2021 | Supplemental Material
Journal Article Open

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


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.

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.

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August 20, 2023
October 23, 2023