Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Fengwang Li; Yuguang C. Li; Ziyun Wang; Jun Li; Dae-Hyun Nam; Yanwei Lum; Mingchuan Luo; Xue Wang; Adnan Ozden; Sung-Fu Hung; Bin Chen; Yuhang Wang; Joshua Wicks; Yi Xu; Yilin Li; Christine M. Gabardo; Cao-Thang Dinh; Ying Wang; Tao-Tao Zhuang; David Sinton; Edward H. Sargent

doi:10.1038/s41929-019-0383-7

Cooperative CO₂-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Fengwang Li, Yuguang C. Li, Ziyun Wang, Jun Li, Dae-Hyun Nam, Yanwei Lum, Mingchuan Luo, Xue Wang, Adnan Ozden, Sung-Fu Hung, Bin Chen, Yuhang Wang, Joshua Wicks, Yi Xu, Yilin Li, Christine M. Gabardo, Cao-Thang Dinh, Ying Wang, Tao-Tao Zhuang, David SintonEdward H. Sargent^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

633 Citations (Scopus)

Abstract

Electrochemical conversion of CO₂ into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO₂ and H₂O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO₂ to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO₂-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm⁻² at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%.

Original language	English
Pages (from-to)	75-82
Journal	Nature Catalysis
Volume	3
Issue number	1
Online published	16 Dec 2019
DOIs	https://doi.org/10.1038/s41929-019-0383-7
Publication status	Published - Jan 2020
Externally published	Yes

Funding

The authors acknowledge funding support from Suncor Energy, the Ontario Research fund and the Natural Sciences and Engineering Research Council (NSERC). DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Niagara supercomputer at the SciNet HPC Consortium and the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario’s Ontario Research Fund – Research Excellence, and the University of Toronto. SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. This research used synchrotron resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory and was supported by the US Department of Energy under contract no. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners. F.L. thanks H.T.L. for ICP–MS measurement. J.L. acknowledges the Banting Postdoctoral Fellowships programme. C.G. acknowledges the NSERC Postdoctoral Fellowships programme. D.S. acknowledges the NSERC E.W.R. Steacie Memorial Fellowship.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy
SDG 13 Climate Action

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Cite this

Li, F., Li, Y. C., Wang, Z., Li, J., Nam, D.-H., Lum, Y., Luo, M., Wang, X., Ozden, A., Hung, S.-F., Chen, B., Wang, Y., Wicks, J., Xu, Y., Li, Y., Gabardo, C. M., Dinh, C.-T., Wang, Y., Zhuang, T.-T., ... Sargent, E. H. (2020). Cooperative CO₂-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nature Catalysis, 3(1), 75-82. https://doi.org/10.1038/s41929-019-0383-7

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title = "Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces",

abstract = "Electrochemical conversion of CO2 into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO2 and H2O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO2 to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO2-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm−2 at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%.",

author = "Fengwang Li and Li, {Yuguang C.} and Ziyun Wang and Jun Li and Dae-Hyun Nam and Yanwei Lum and Mingchuan Luo and Xue Wang and Adnan Ozden and Sung-Fu Hung and Bin Chen and Yuhang Wang and Joshua Wicks and Yi Xu and Yilin Li and Gabardo, {Christine M.} and Cao-Thang Dinh and Ying Wang and Tao-Tao Zhuang and David Sinton and Sargent, {Edward H.}",

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Li, F, Li, YC, Wang, Z, Li, J, Nam, D-H, Lum, Y, Luo, M, Wang, X, Ozden, A, Hung, S-F, Chen, B, Wang, Y, Wicks, J, Xu, Y, Li, Y, Gabardo, CM, Dinh, C-T, Wang, Y, Zhuang, T-T, Sinton, D & Sargent, EH 2020, 'Cooperative CO₂-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces', Nature Catalysis, vol. 3, no. 1, pp. 75-82. https://doi.org/10.1038/s41929-019-0383-7

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AU - Li, Fengwang

AU - Li, Yuguang C.

AU - Wang, Ziyun

AU - Li, Jun

AU - Nam, Dae-Hyun

AU - Lum, Yanwei

AU - Luo, Mingchuan

AU - Wang, Xue

AU - Ozden, Adnan

AU - Hung, Sung-Fu

AU - Chen, Bin

AU - Wang, Yuhang

AU - Wicks, Joshua

AU - Xu, Yi

AU - Li, Yilin

AU - Gabardo, Christine M.

AU - Dinh, Cao-Thang

AU - Wang, Ying

AU - Zhuang, Tao-Tao

AU - Sinton, David

AU - Sargent, Edward H.

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N2 - Electrochemical conversion of CO2 into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO2 and H2O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO2 to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO2-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm−2 at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%.

AB - Electrochemical conversion of CO2 into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO2 and H2O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO2 to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO2-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm−2 at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%.

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