Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products

doi:10.1021/acscatal.7b03477

Title: Mechanism of CO ₂ Reduction at Copper Surfaces: Pathways to C ₂ Products

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Abstract

On the basis of constraints from reported experimental observations and density functional theory simulations, in this paper we propose a mechanism for the reduction of CO ₂ to C ₂ products on copper electrodes. To model the effects of an applied potential bias on the reactions, calculations are carried out with a variable, fractional number of electrons on the unit cell, which is optimized so that the Fermi level matches the actual chemical potential of electrons (i.e., the applied bias); an implicit electrolyte model allows for compensation of the surface charge so that neutrality is maintained in the overall simulation cell. Our mechanism explains the presence of the seven C ₂ species that have been detected in the reaction, as well as other notable experimental observations. Furthermore, our results shed light on the difference in activities toward C ₂ products between the (100) and (111) facets of copper. Finally, we compare our methodologies and findings with those in other recent mechanistic studies of the copper-catalyzed CO ₂ reduction reaction.

Authors:

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

Publication Date:: 2018-01-11

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1464161

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

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; artificial photosynthesis; DFT; electrocatalysis; ethanol; ethylene; mechanisms

Citation Formats


                    Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products.  United States: N. p., 2018. 
        Web.  doi:10.1021/acscatal.7b03477.

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                    Garza, Alejandro J., Bell, Alexis T., & Head-Gordon, Martin. Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products.  United States.  doi:10.1021/acscatal.7b03477.

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                    Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Thu .  
        "Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products".  United States.  doi:10.1021/acscatal.7b03477.  https://www.osti.gov/servlets/purl/1464161.

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@article{osti_1464161,

  title        = {Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products},

  author       = {Garza, Alejandro J. and Bell, Alexis T. and Head-Gordon, Martin},

  abstractNote = {On the basis of constraints from reported experimental observations and density functional theory simulations, in this paper we propose a mechanism for the reduction of CO2 to C2 products on copper electrodes. To model the effects of an applied potential bias on the reactions, calculations are carried out with a variable, fractional number of electrons on the unit cell, which is optimized so that the Fermi level matches the actual chemical potential of electrons (i.e., the applied bias); an implicit electrolyte model allows for compensation of the surface charge so that neutrality is maintained in the overall simulation cell. Our mechanism explains the presence of the seven C2 species that have been detected in the reaction, as well as other notable experimental observations. Furthermore, our results shed light on the difference in activities toward C2 products between the (100) and (111) facets of copper. Finally, we compare our methodologies and findings with those in other recent mechanistic studies of the copper-catalyzed CO2 reduction reaction.},

  doi          = {10.1021/acscatal.7b03477},

  journal      = {ACS Catalysis},

  number       = 2,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {1}

}

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DOI: 10.1021/acscatal.7b03477

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Title: Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products

Abstract

Citation Formats

Title: Mechanism of CO ₂ Reduction at Copper Surfaces: Pathways to C ₂ Products