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Title: Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility

Abstract

Steering the selectivity of Cu-based electrochemical CO2 reduction (CO2R) catalysts toward targeted products will serve to improve the technoeconomic outlook of technologies based on this process. Using physical vapor deposition as a tool to overcome thermodynamic miscibility limitations, CuAg thin films with nonequilibrium Cu/Ag alloying were prepared for CO2R performance evaluation. In comparison to pure Cu, the CuAg thin films showed significantly higher activity and selectivity toward liquid carbonyl products, including acetaldehyde and acetate. Suppressed activity and selectivity toward hydrocarbons and the competing hydrogen evolution were also demonstrated on CuAg thin films, with a greater degree of suppression observed at increasing nominal Ag compositions. Compositional-dependent CO2R trends coupled with physical characterization and density functional theory suggest that significant miscibility of Ag into the Cu-rich phase of the catalyst underpinned the observed CO2R trends through tuning of adsorbate and reaction intermediate binding energies on the surface.

Authors:
ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490965
Alternate Identifier(s):
OSTI ID: 1490728
Grant/Contract Number:  
AC02-76SF00515; P2ELP2_168600; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 3; Journal Issue: 12; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Higgins, Drew, Landers, Alan T., Ji, Yongfei, Nitopi, Stephanie, Morales-Guio, Carlos G., Wang, Lei, Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F.. Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility. United States: N. p., 2018. Web. https://doi.org/10.1021/acsenergylett.8b01736.
Higgins, Drew, Landers, Alan T., Ji, Yongfei, Nitopi, Stephanie, Morales-Guio, Carlos G., Wang, Lei, Chan, Karen, Hahn, Christopher, & Jaramillo, Thomas F.. Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility. United States. https://doi.org/10.1021/acsenergylett.8b01736
Higgins, Drew, Landers, Alan T., Ji, Yongfei, Nitopi, Stephanie, Morales-Guio, Carlos G., Wang, Lei, Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F.. Mon . "Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility". United States. https://doi.org/10.1021/acsenergylett.8b01736. https://www.osti.gov/servlets/purl/1490965.
@article{osti_1490965,
title = {Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility},
author = {Higgins, Drew and Landers, Alan T. and Ji, Yongfei and Nitopi, Stephanie and Morales-Guio, Carlos G. and Wang, Lei and Chan, Karen and Hahn, Christopher and Jaramillo, Thomas F.},
abstractNote = {Steering the selectivity of Cu-based electrochemical CO2 reduction (CO2R) catalysts toward targeted products will serve to improve the technoeconomic outlook of technologies based on this process. Using physical vapor deposition as a tool to overcome thermodynamic miscibility limitations, CuAg thin films with nonequilibrium Cu/Ag alloying were prepared for CO2R performance evaluation. In comparison to pure Cu, the CuAg thin films showed significantly higher activity and selectivity toward liquid carbonyl products, including acetaldehyde and acetate. Suppressed activity and selectivity toward hydrocarbons and the competing hydrogen evolution were also demonstrated on CuAg thin films, with a greater degree of suppression observed at increasing nominal Ag compositions. Compositional-dependent CO2R trends coupled with physical characterization and density functional theory suggest that significant miscibility of Ag into the Cu-rich phase of the catalyst underpinned the observed CO2R trends through tuning of adsorbate and reaction intermediate binding energies on the surface.},
doi = {10.1021/acsenergylett.8b01736},
journal = {ACS Energy Letters},
number = 12,
volume = 3,
place = {United States},
year = {2018},
month = {11}
}

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