skip to main content

DOE PAGESDOE PAGES

Title: Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ;  [1] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231; SC0004993
Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 26; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; suboxide copper; ambient pressure XPS; density functional theory; M06L
OSTI Identifier:
1363709
Alternate Identifier(s):
OSTI ID: 1408437

Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, and Crumlin, Ethan J.. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. United States: N. p., Web. doi:10.1073/pnas.1701405114.
Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, & Crumlin, Ethan J.. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. United States. doi:10.1073/pnas.1701405114.
Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, and Crumlin, Ethan J.. 2017. "Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2". United States. doi:10.1073/pnas.1701405114.
@article{osti_1363709,
title = {Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2},
author = {Favaro, Marco and Xiao, Hai and Cheng, Tao and Goddard, William A. and Yano, Junko and Crumlin, Ethan J.},
abstractNote = {A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.},
doi = {10.1073/pnas.1701405114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 26,
volume = 114,
place = {United States},
year = {2017},
month = {6}
}

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.
  • Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234
  • DOI: 10.1021/ja3010978

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993