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Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

Abstract

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 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 × 10 3 s –1. Oxygen can survive longer in deeper layers, but it does not promote CO 2 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 CO 2 adsorption on copper.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. 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) (SC-22)
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. doi: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. doi: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 = {2018},
month = {1}
}

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Figures / Tables:

Figure 1 Figure 1: Free energy profile (in eV) for migration of an oxygen atom occupying a tetrahedral site below the surface to a hole site on the surface at various potentials (θ = ¼, pH = 7).

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