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Selective reduction of CO to acetaldehyde with CuAg electrocatalysts
Abstract
Electrochemical CO reduction can serve as a sequential step in the transformation of CO 2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of −0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1594223
- Grant/Contract Number:
- SC0004993
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. United States: N. p., 2020.
Web. doi:10.1073/pnas.1821683117.
Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, & Jaramillo, Thomas F. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. United States. doi:10.1073/pnas.1821683117.
Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F. Fri .
"Selective reduction of CO to acetaldehyde with CuAg electrocatalysts". United States. doi:10.1073/pnas.1821683117.
@article{osti_1594223,
title = {Selective reduction of CO to acetaldehyde with CuAg electrocatalysts},
author = {Wang, Lei and Higgins, Drew C. and Ji, Yongfei and Morales-Guio, Carlos G. and Chan, Karen and Hahn, Christopher and Jaramillo, Thomas F.},
abstractNote = {Electrochemical CO reduction can serve as a sequential step in the transformation of CO 2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of −0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.},
doi = {10.1073/pnas.1821683117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {1}
}
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