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Title: Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites

Abstract

The electroreduction of C1 feedgas to high-energy-density fuels provides an attractive avenue to the storage of renewable electricity. Much progress has been made to improve selectivity to C1 and C2 products, however, the selectivity to desirable high-energy-density C3 products remains relatively low. We reason that C3 electrosynthesis relies on a higher-order reaction pathway that requires the formation of multiple carbon-carbon (C-C) bonds, and thus pursue a strategy explicitly designed to couple C2 with C1 intermediates. We develop an approach wherein neighboring copper atoms having distinct electronic structures interact with two adsorbates to catalyze an asymmetric reaction. We achieve a record n-propanol Faradaic efficiency (FE) of (33 ± 1)% with a conversion rate of (4.5 ± 0.1) mA cm–2, and a record n-propanol cathodic energy conversion efficiency (EEcathodic half-cell) of 21%. The FE and EEcathodic half-cell represent a 1.3× improvement relative to previously-published CO-to-n-propanol electroreduction reports.

Authors:
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  1. Univ. of Toronto, ON (Canada)
  2. Industrial Technology Research Inst., Hsinchu (Taiwan)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
Ontario Research Fund Research; Natural Sciences and Engineering Research Council of Canada (NSERC); CIFAR Bio-Inspired Solar Energy; University of Toronto Connaught; USDOE Office of Science (SC); Federal Economic Development Agency of Southern Ontario; Province of Ontario; IBM Canada Ltd.; Ontario Centres of Excellence; Mitacs; Canada Foundation for Innovation (CFI); Ontario Research Fund; Banting Postdoctoral Fellowships Program
OSTI Identifier:
1624214
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; science & technology - other topics; carbon capture and storage; electrocatalysis; materials for energy and catalysis; renewable energy

Citation Formats

Wang, Xue, Wang, Ziyun, Zhuang, Tao-Tao, Dinh, Cao-Thang, Li, Jun, Nam, Dae-Hyun, Li, Fengwang, Huang, Chun-Wei, Tan, Chih-Shan, Chen, Zitao, Chi, Miaofang, Gabardo, Christine M., Seifitokaldani, Ali, Todorović, Petar, Proppe, Andrew, Pang, Yuanjie, Kirmani, Ahmad R., Wang, Yuhang, Ip, Alexander H., Richter, Lee J., Scheffel, Benjamin, Xu, Aoni, Lo, Shen-Chuan, Kelley, Shana O., Sinton, David, and Sargent, Edward H. Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites. United States: N. p., 2019. Web. https://doi.org/10.1038/s41467-019-13190-6.
Wang, Xue, Wang, Ziyun, Zhuang, Tao-Tao, Dinh, Cao-Thang, Li, Jun, Nam, Dae-Hyun, Li, Fengwang, Huang, Chun-Wei, Tan, Chih-Shan, Chen, Zitao, Chi, Miaofang, Gabardo, Christine M., Seifitokaldani, Ali, Todorović, Petar, Proppe, Andrew, Pang, Yuanjie, Kirmani, Ahmad R., Wang, Yuhang, Ip, Alexander H., Richter, Lee J., Scheffel, Benjamin, Xu, Aoni, Lo, Shen-Chuan, Kelley, Shana O., Sinton, David, & Sargent, Edward H. Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites. United States. https://doi.org/10.1038/s41467-019-13190-6
Wang, Xue, Wang, Ziyun, Zhuang, Tao-Tao, Dinh, Cao-Thang, Li, Jun, Nam, Dae-Hyun, Li, Fengwang, Huang, Chun-Wei, Tan, Chih-Shan, Chen, Zitao, Chi, Miaofang, Gabardo, Christine M., Seifitokaldani, Ali, Todorović, Petar, Proppe, Andrew, Pang, Yuanjie, Kirmani, Ahmad R., Wang, Yuhang, Ip, Alexander H., Richter, Lee J., Scheffel, Benjamin, Xu, Aoni, Lo, Shen-Chuan, Kelley, Shana O., Sinton, David, and Sargent, Edward H. Fri . "Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites". United States. https://doi.org/10.1038/s41467-019-13190-6. https://www.osti.gov/servlets/purl/1624214.
@article{osti_1624214,
title = {Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites},
author = {Wang, Xue and Wang, Ziyun and Zhuang, Tao-Tao and Dinh, Cao-Thang and Li, Jun and Nam, Dae-Hyun and Li, Fengwang and Huang, Chun-Wei and Tan, Chih-Shan and Chen, Zitao and Chi, Miaofang and Gabardo, Christine M. and Seifitokaldani, Ali and Todorović, Petar and Proppe, Andrew and Pang, Yuanjie and Kirmani, Ahmad R. and Wang, Yuhang and Ip, Alexander H. and Richter, Lee J. and Scheffel, Benjamin and Xu, Aoni and Lo, Shen-Chuan and Kelley, Shana O. and Sinton, David and Sargent, Edward H.},
abstractNote = {The electroreduction of C1 feedgas to high-energy-density fuels provides an attractive avenue to the storage of renewable electricity. Much progress has been made to improve selectivity to C1 and C2 products, however, the selectivity to desirable high-energy-density C3 products remains relatively low. We reason that C3 electrosynthesis relies on a higher-order reaction pathway that requires the formation of multiple carbon-carbon (C-C) bonds, and thus pursue a strategy explicitly designed to couple C2 with C1 intermediates. We develop an approach wherein neighboring copper atoms having distinct electronic structures interact with two adsorbates to catalyze an asymmetric reaction. We achieve a record n-propanol Faradaic efficiency (FE) of (33 ± 1)% with a conversion rate of (4.5 ± 0.1) mA cm–2, and a record n-propanol cathodic energy conversion efficiency (EEcathodic half-cell) of 21%. The FE and EEcathodic half-cell represent a 1.3× improvement relative to previously-published CO-to-n-propanol electroreduction reports.},
doi = {10.1038/s41467-019-13190-6},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {11}
}

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Figures / Tables:

Fig. 1 Fig. 1 : DFT calculations on C1–C1 and C1–C2 coupling. DFT calculated reaction barriers (Ea) for C1–C1 and C1–C2 coupling on screened M-doped Cu systems (M=Ag, Au, Ru, Rh, and Pd). The geometries of M-doped Cu surface, C1, C2, and C3 on M-doped Cu are shown with the corresponding labels,more » respectively. Cu, M, C, and O are illustrated as orange, light blue, gray, and red balls, respectively, while water molecules are shown as lines« less

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