Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?

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

doi:10.1021/acs.jpclett.7b03180

Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?

Journal Article · Wed Jan 17 00:00:00 EST 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b03180· OSTI ID:1430685

Garza, Alejandro J. ^[1];

^[2];

^[3]

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

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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1430685

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 3; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 105 works

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