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Title: Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts

Abstract

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulk of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [4];  [2];  [2];  [2];  [2];  [5];  [5];  [4];  [3]; ORCiD logo [6]
  1. Ruhr Univ., Bochum (Germany). Dept. of Physics; Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics
  2. Ruhr Univ., Bochum (Germany). Dept. of Physics
  3. Univ. of Copenhagen (Denmark). Dept. of Chemistry
  4. Univ. of Pittsburgh, PA (United States). Chemical and Petroleum Engineering and Physics
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  6. Ruhr Univ., Bochum (Germany). Dept. of Physics; Fritz-Haber Inst. of the Max Planck Society, Berlin (Germany). Dept. of Interface Science
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Pittsburgh, PA (United States); Ruhr Univ., Bochum (Germany); Univ. of Copenhagen (Denmark)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); German Federal Ministry of Education and Research (BMBF); German Research Foundation (DFG); European Research Council (ERC); Carlsberg Foundation (Denmark)
OSTI Identifier:
1433976
Alternate Identifier(s):
OSTI ID: 1374676
Report Number(s):
BNL-203511-2018-JAAM
Journal ID: ISSN 0044-8249
Grant/Contract Number:  
SC0012704; AC02-06CH11357; FG02-03ER15476; CHEM 1213182; CHE-1534630; 03SF0523C; ERC-725915; CF15-0165
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 38; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mistry, Hemma, Choi, Yong-Wook, Bagger, Alexander, Scholten, Fabian, Bonifacio, Cecile S., Sinev, Ilya, Divins, Nuria J., Zegkinoglou, Ioannis, Jeon, Hyo Sang, Kisslinger, Kim, Stach, Eric A., Yang, Judith C., Rossmeisl, Jan, and Roldan Cuenya, Beatriz. Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts. United States: N. p., 2017. Web. doi:10.1002/ange.201704613.
Mistry, Hemma, Choi, Yong-Wook, Bagger, Alexander, Scholten, Fabian, Bonifacio, Cecile S., Sinev, Ilya, Divins, Nuria J., Zegkinoglou, Ioannis, Jeon, Hyo Sang, Kisslinger, Kim, Stach, Eric A., Yang, Judith C., Rossmeisl, Jan, & Roldan Cuenya, Beatriz. Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts. United States. doi:10.1002/ange.201704613.
Mistry, Hemma, Choi, Yong-Wook, Bagger, Alexander, Scholten, Fabian, Bonifacio, Cecile S., Sinev, Ilya, Divins, Nuria J., Zegkinoglou, Ioannis, Jeon, Hyo Sang, Kisslinger, Kim, Stach, Eric A., Yang, Judith C., Rossmeisl, Jan, and Roldan Cuenya, Beatriz. Fri . "Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts". United States. doi:10.1002/ange.201704613. https://www.osti.gov/servlets/purl/1433976.
@article{osti_1433976,
title = {Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts},
author = {Mistry, Hemma and Choi, Yong-Wook and Bagger, Alexander and Scholten, Fabian and Bonifacio, Cecile S. and Sinev, Ilya and Divins, Nuria J. and Zegkinoglou, Ioannis and Jeon, Hyo Sang and Kisslinger, Kim and Stach, Eric A. and Yang, Judith C. and Rossmeisl, Jan and Roldan Cuenya, Beatriz},
abstractNote = {Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulk of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO2 electroreduction.},
doi = {10.1002/ange.201704613},
journal = {Angewandte Chemie},
number = 38,
volume = 129,
place = {United States},
year = {2017},
month = {7}
}

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Works referenced in this record:

CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films
journal, April 2012

  • Li, Christina W.; Kanan, Matthew W.
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  • Whipple, Devin T.; Kenis, Paul J. A.
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