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Title: Sequential catalysis controls selectivity in electrochemical CO 2 reduction on Cu

Abstract

Electrochemical reduction of CO 2 in aqueous media is a strategy for sustainable production of fuels and commodity chemicals. Cu is the only catalyst which converts CO 2 to significant quantities of hydrocarbons and oxygenates. Here we demonstrate that oxygenate products can be favored over hydrocarbons by positioning a local source of CO generated by a CO producing catalyst (Au or Ag) in close proximity to a Cu catalyst. Use of a bimetallic device comprising interdigitated and independently controllable lines of Au and Cu allows the local CO concentration to be modulated. Notably, diffusional simulations show that the saturation concentration of CO can be exceeded locally. Actuating both the Au and Cu lines increases the oxygenate to ethylene ratio compared to actuating Cu only. Increasing the relative area of CO-producing Au relative to Cu also increases this ratio. These insights are translated into a second bimetallic system comprising Cu dots/lines patterned directly onto a Ag substrate, allowing for the distance between Cu and the CO generating metal to be precisely controlled. Controlling the relative areas of Ag and Cu allows for tuning of the oxygenate to ethylene ratio from 0.59 to 2.39 and an increase in oxygenate faradaic efficiency frommore » 21.4% to 41.4%, while maintaining the selectivity to C 2/C 3 products in the 50–65% range. We attribute this change in selectivity to be due to an increased *CO coverage on Cu. Finally, by utilizing diffusional transport of CO to the Cu, a sequential catalysis pathway is created which allows for the control of oxygenate selectivity in aqueous CO 2 reduction.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Materials Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
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:
1560561
Alternate Identifier(s):
OSTI ID: 1460876
Grant/Contract Number:  
AC02-05CH11231; SC0004993; CHE-080405
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 10; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lum, Yanwei, and Ager, Joel W. Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. United States: N. p., 2018. Web. doi:10.1039/c8ee01501e.
Lum, Yanwei, & Ager, Joel W. Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. United States. https://doi.org/10.1039/c8ee01501e
Lum, Yanwei, and Ager, Joel W. Fri . "Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu". United States. https://doi.org/10.1039/c8ee01501e. https://www.osti.gov/servlets/purl/1560561.
@article{osti_1560561,
title = {Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu},
author = {Lum, Yanwei and Ager, Joel W.},
abstractNote = {Electrochemical reduction of CO2 in aqueous media is a strategy for sustainable production of fuels and commodity chemicals. Cu is the only catalyst which converts CO2 to significant quantities of hydrocarbons and oxygenates. Here we demonstrate that oxygenate products can be favored over hydrocarbons by positioning a local source of CO generated by a CO producing catalyst (Au or Ag) in close proximity to a Cu catalyst. Use of a bimetallic device comprising interdigitated and independently controllable lines of Au and Cu allows the local CO concentration to be modulated. Notably, diffusional simulations show that the saturation concentration of CO can be exceeded locally. Actuating both the Au and Cu lines increases the oxygenate to ethylene ratio compared to actuating Cu only. Increasing the relative area of CO-producing Au relative to Cu also increases this ratio. These insights are translated into a second bimetallic system comprising Cu dots/lines patterned directly onto a Ag substrate, allowing for the distance between Cu and the CO generating metal to be precisely controlled. Controlling the relative areas of Ag and Cu allows for tuning of the oxygenate to ethylene ratio from 0.59 to 2.39 and an increase in oxygenate faradaic efficiency from 21.4% to 41.4%, while maintaining the selectivity to C2/C3 products in the 50–65% range. We attribute this change in selectivity to be due to an increased *CO coverage on Cu. Finally, by utilizing diffusional transport of CO to the Cu, a sequential catalysis pathway is created which allows for the control of oxygenate selectivity in aqueous CO2 reduction.},
doi = {10.1039/c8ee01501e},
url = {https://www.osti.gov/biblio/1560561}, journal = {Energy & Environmental Science},
issn = {1754-5692},
number = 10,
volume = 11,
place = {United States},
year = {2018},
month = {7}
}

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Cited by: 9 works
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Works referenced in this record:

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    Works referencing / citing this record:

    Electrochemical Carbon Dioxide Splitting
    journal, February 2019


    Unveiling Electrochemical Reaction Pathways of CO 2 Reduction to C N Species at S‐Vacancies of MoS 2
    journal, May 2019


    Rational Design of Ag‐Based Catalysts for the Electrochemical CO 2 Reduction to CO: A Review
    journal, December 2019


    Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products
    journal, March 2019


    From CO 2 methanation to ambitious long-chain hydrocarbons: alternative fuels paving the path to sustainability
    journal, January 2019