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Title: Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity

Abstract

The electrochemical reduction of carbon dioxide using renewably generated electricity offers a potential means for producing fuels and chemicals in a sustainable manner. To date, copper has been found to be the most effective catalyst for electrochemically reducing carbon dioxide to products such as methane, ethene, and ethanol. Unfortunately, the current efficiency of the process is limited by competition with the relatively facile hydrogen evolution reaction. Since multi-carbon products are more valuable precursors to chemicals and fuels than methane, there is considerable interest in modifying copper to enhance the multi-carbon product selectivity. In this paper, we report our investigations of electrochemical carbon dioxide reduction over CuAg bimetallic electrodes and surface alloys, which we find to be more selective for the formation of multi-carbon products than pure copper. This selectivity enhancement is a result of the selective suppression of hydrogen evolution, which occurs due to compressive strain induced by the formation of a CuAg surface alloy. Furthermore, we report that these bimetallic electrocatalysts exhibit an unusually high selectivity for the formation of multi-carbon carbonyl-containing products, which we hypothesize to be the consequence of a reduced coverage of adsorbed hydrogen and the reduced oxophilicity of the compressively strained copper. Thus and finally,more » we show that promoting copper surface with small amounts of Ag is a promising means for improving the multi-carbon oxygenated product selectivity of copper during electrochemical CO2 reduction.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, 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); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1463311
Alternate Identifier(s):
OSTI ID: 1436343
Grant/Contract Number:  
AC02-76SF00515; SC0004993; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 44; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Clark, Ezra L., Hahn, Christopher, Jaramillo, Thomas F., and Bell, Alexis T. Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity. United States: N. p., 2017. Web. doi:10.1021/jacs.7b08607.
Clark, Ezra L., Hahn, Christopher, Jaramillo, Thomas F., & Bell, Alexis T. Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity. United States. doi:10.1021/jacs.7b08607.
Clark, Ezra L., Hahn, Christopher, Jaramillo, Thomas F., and Bell, Alexis T. Sat . "Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity". United States. doi:10.1021/jacs.7b08607. https://www.osti.gov/servlets/purl/1463311.
@article{osti_1463311,
title = {Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity},
author = {Clark, Ezra L. and Hahn, Christopher and Jaramillo, Thomas F. and Bell, Alexis T.},
abstractNote = {The electrochemical reduction of carbon dioxide using renewably generated electricity offers a potential means for producing fuels and chemicals in a sustainable manner. To date, copper has been found to be the most effective catalyst for electrochemically reducing carbon dioxide to products such as methane, ethene, and ethanol. Unfortunately, the current efficiency of the process is limited by competition with the relatively facile hydrogen evolution reaction. Since multi-carbon products are more valuable precursors to chemicals and fuels than methane, there is considerable interest in modifying copper to enhance the multi-carbon product selectivity. In this paper, we report our investigations of electrochemical carbon dioxide reduction over CuAg bimetallic electrodes and surface alloys, which we find to be more selective for the formation of multi-carbon products than pure copper. This selectivity enhancement is a result of the selective suppression of hydrogen evolution, which occurs due to compressive strain induced by the formation of a CuAg surface alloy. Furthermore, we report that these bimetallic electrocatalysts exhibit an unusually high selectivity for the formation of multi-carbon carbonyl-containing products, which we hypothesize to be the consequence of a reduced coverage of adsorbed hydrogen and the reduced oxophilicity of the compressively strained copper. Thus and finally, we show that promoting copper surface with small amounts of Ag is a promising means for improving the multi-carbon oxygenated product selectivity of copper during electrochemical CO2 reduction.},
doi = {10.1021/jacs.7b08607},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 139,
place = {United States},
year = {2017},
month = {10}
}

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Regulating C–C coupling in thermocatalytic and electrocatalytic CO x conversion based on surface science
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