Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?
Abstract
It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 103 s–1. Oxygen can survive longer in deeper layers, but it does not promote CO2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO2 adsorption on copper.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1430685
- Grant/Contract Number:
- AC02-05CH11231; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.7b03180.
Garza, Alejandro J., Bell, Alexis T., & Head-Gordon, Martin. Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?. United States. https://doi.org/10.1021/acs.jpclett.7b03180
Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Wed .
"Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?". United States. https://doi.org/10.1021/acs.jpclett.7b03180. https://www.osti.gov/servlets/purl/1430685.
@article{osti_1430685,
title = {Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?},
author = {Garza, Alejandro J. and Bell, Alexis T. and Head-Gordon, Martin},
abstractNote = {It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 103 s–1. Oxygen can survive longer in deeper layers, but it does not promote CO2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO2 adsorption on copper.},
doi = {10.1021/acs.jpclett.7b03180},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 9,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2018},
month = {Wed Jan 17 00:00:00 EST 2018}
}
Web of Science
Figures / Tables:
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