This content will become publicly available on Sat Feb 08 00:00:00 EST 2025
Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts
Abstract
Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C2 product specificity during electrocatalytic CO2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm-2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO2 electroreduction to a single C2 product.
- Authors:
-
[1];
[1];
[4];
[3];
[3];
[3];
[7];
[8];
[2];
[1]
- University of Cincinnati, OH (United States)
- Rice University, Houston, TX (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Stony Brook University, NY (United States)
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source (NSLS)
- Stony Brook University, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Arizona State University, Tempe, AZ (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)
- OSTI Identifier:
- 2301665
- Grant/Contract Number:
- AC05-00OR22725; SC0012704; SC0012335; EE0010836; CBET-2033343; CBET-2143941; ECCS-1542160; CHE 2102299
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Chemical Engineering
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 2; Journal ID: ISSN 2948-1198
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon capture and storage; chemical engineering; electrocatalysis
Citation Formats
Li, Zhengyuan, Wang, Peng, Lyu, Xiang, Kondapalli, Vamsi Reddy, Xiang, Shuting, Jimenez, Juan D., Ma, Lu, Ito, Takeshi, Zhang, Tianyu, Raj, Jithu, Fang, Yanbo, Bai, Yaocai, Li, Jianlin, Serov, Alexey, Shanov, Vesselin, Frenkel, Anatoly I., Senanayake, Sanjaya D., Yang, Shize, Senftle, Thomas P., and Wu, Jingjie. Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts. United States: N. p., 2024.
Web. doi:10.1038/s44286-023-00018-w.
Li, Zhengyuan, Wang, Peng, Lyu, Xiang, Kondapalli, Vamsi Reddy, Xiang, Shuting, Jimenez, Juan D., Ma, Lu, Ito, Takeshi, Zhang, Tianyu, Raj, Jithu, Fang, Yanbo, Bai, Yaocai, Li, Jianlin, Serov, Alexey, Shanov, Vesselin, Frenkel, Anatoly I., Senanayake, Sanjaya D., Yang, Shize, Senftle, Thomas P., & Wu, Jingjie. Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts. United States. https://doi.org/10.1038/s44286-023-00018-w
Li, Zhengyuan, Wang, Peng, Lyu, Xiang, Kondapalli, Vamsi Reddy, Xiang, Shuting, Jimenez, Juan D., Ma, Lu, Ito, Takeshi, Zhang, Tianyu, Raj, Jithu, Fang, Yanbo, Bai, Yaocai, Li, Jianlin, Serov, Alexey, Shanov, Vesselin, Frenkel, Anatoly I., Senanayake, Sanjaya D., Yang, Shize, Senftle, Thomas P., and Wu, Jingjie. Thu .
"Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts". United States. https://doi.org/10.1038/s44286-023-00018-w.
@article{osti_2301665,
title = {Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts},
author = {Li, Zhengyuan and Wang, Peng and Lyu, Xiang and Kondapalli, Vamsi Reddy and Xiang, Shuting and Jimenez, Juan D. and Ma, Lu and Ito, Takeshi and Zhang, Tianyu and Raj, Jithu and Fang, Yanbo and Bai, Yaocai and Li, Jianlin and Serov, Alexey and Shanov, Vesselin and Frenkel, Anatoly I. and Senanayake, Sanjaya D. and Yang, Shize and Senftle, Thomas P. and Wu, Jingjie},
abstractNote = {Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C2 product specificity during electrocatalytic CO2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm-2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO2 electroreduction to a single C2 product.},
doi = {10.1038/s44286-023-00018-w},
journal = {Nature Chemical Engineering},
number = 2,
volume = 1,
place = {United States},
year = {Thu Feb 08 00:00:00 EST 2024},
month = {Thu Feb 08 00:00:00 EST 2024}
}
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