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

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

doi:10.1021/acs.jpclett.7b03180

Cited by 148CO2 Reduction Techniques and CatalystsElectrocatalysts for Energy ConversionCatalysts for Methane Reforming

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

Garza, Alejandro J., Bell, Alexis T., Head-Gordon, Martin·2018·The Journal of Physical Chemistry Letters

DOI 10.1021/acs.jpclett.7b03180

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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. 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 × 10 7 s –1 ). Once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.

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Authors: Garza, A. J., Bell, A. T., & Head-Gordon, M.
Affiliations: Lawrence Berkeley National Laboratory (US)
Corresponding author: Bell, Alexis T.
ORCID: Garza, Alejandro J.
Bell, Alexis T.
Head-Gordon, Martin
Venue: The Journal of Physical Chemistry Letters
Publisher: American Chemical Society (ACS)
Published: 2018-01-19
Volume: 9
Issue: 3
Pages: 601-606
ISSN: 1948-7185 (ISSN-L)
DOI: 10.1021/acs.jpclett.7b03180
OpenAlex: W2782968955
Cited by: 148
References: 52
Citations by year: 2026: 6 · 2025: 10 · 2024: 16 · 2023: 7 · 2022: 20 · 2021: 24 · 2020: 22 · 2019: 27 · 2018: 16
FWCI: 5.13
Type: journal article
Language: en
Open access: closed
Locations: The Journal of Physical Chemistry Letters (publishedVersion)
PubMed (publishedVersion)
eScholarship (California Digital Library) (submittedVersion)
OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders: Basic Energy Sciences (DE-SC00004993)
Topics: Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
Keywords: subsurface oxygen, electrochemical CO2 reduction, copper electrocatalysis, oxygen diffusion, oxygen adsorption, Cu(111), Cu(100), crystal facets, interstitial sites, surface stability, dispersion interactions

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

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