The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction

doi:10.1021/acs.jpcc.8b04983

Title: The Role of Subsurface Oxygen on Cu Surfaces for CO₂ Electrochemical Reduction

Abstract

Under ambient conditions, copper with oxygen near the surface displays strengthened CO₂ and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO₂ reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity of crystalline Cu.

Authors:

Fields, Meredith ^[1]; Hong, Xin ^[2]; Norskov, Jens K. ^[1]; Chan, Karen ^[3]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Zhejiang Univ., Hangzhou (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: 2018-06-12

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1457147

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 28; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Fields, Meredith, Hong, Xin, Norskov, Jens K., and Chan, Karen. The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.jpcc.8b04983.

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                    Fields, Meredith, Hong, Xin, Norskov, Jens K., & Chan, Karen. The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction.  United States.  doi:10.1021/acs.jpcc.8b04983.

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                    Fields, Meredith, Hong, Xin, Norskov, Jens K., and Chan, Karen. Tue .  
        "The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction".  United States.  doi:10.1021/acs.jpcc.8b04983.  https://www.osti.gov/servlets/purl/1457147.

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@article{osti_1457147,

  title        = {The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction},

  author       = {Fields, Meredith and Hong, Xin and Norskov, Jens K. and Chan, Karen},

  abstractNote = {Under ambient conditions, copper with oxygen near the surface displays strengthened CO2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity of crystalline Cu.},

  doi          = {10.1021/acs.jpcc.8b04983},

  journal      = {Journal of Physical Chemistry. C},

  number       = 28,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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Journal Article:

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DOI: 10.1021/acs.jpcc.8b04983

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Cited by: 5 works

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Figures / Tables:

Table 1: Oxygen Free Energies in a Cu (111) slab.

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Works referencing / citing this record:

Electrochemical CO ₂ Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design
journal, December 2018

Kibria, Md Golam; Edwards, Jonathan P.; Gabardo, Christine M.
Advanced Materials, Vol. 31, Issue 31
DOI: 10.1002/adma.201807166

Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction
journal, June 2019

Martić, Nemanja; Reller, Christian; Macauley, Chandra
Advanced Energy Materials, Vol. 9, Issue 29
DOI: 10.1002/aenm.201901228

Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
journal, September 2019

Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C.
Nature Energy, Vol. 4, Issue 9
DOI: 10.1038/s41560-019-0450-y

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Similar Records

Title: The Role of Subsurface Oxygen on Cu Surfaces for CO2 Electrochemical Reduction

Abstract

Citation Formats

Figures / Tables:

Electrochemical CO 2 Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design journal, December 2018

Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction journal, June 2019

Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels journal, September 2019

Title: The Role of Subsurface Oxygen on Cu Surfaces for CO₂ Electrochemical Reduction

Electrochemical CO ₂ Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design
journal, December 2018

Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction
journal, June 2019

Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
journal, September 2019