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

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 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.

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)
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.
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.
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.
@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}
}

Journal Article:
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Citation Metrics:
Cited by: 43 works
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Figures / Tables:

Figure 1: Figure 1:: Proposed mechanism for the reduction of CO to C2 products at high potentials on Cu(100). Calculated free energies (eV) are the numbers parallel to reaction arrows, where ∆G values at U = 0 V using the CHE appear in standard font (steps involving H+ + e can bemore » corrected to U = −1 V by subtracting 1 eV). ∆G values at U = −1 V using the CEP (at pH = 7) appear in bold font. The seven C2 products of CO2 reduction on copper are highlighted in green. Calculated free energy barriers (eV) are provided for the critical reductive step from intermediate 3 to either 4a or 4b that determines selectivity between the pathway to ethylene (purple) and ethanol (blue).« less

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Works referencing / citing this record:

Structure‐Sensitivity and Electrolyte Effects in CO 2 Electroreduction: From Model Studies to Applications
journal, June 2019

  • Sebastián‐Pascual, Paula; Mezzavilla, Stefano; Stephens, Ifan E. L.
  • ChemCatChem, Vol. 11, Issue 16
  • DOI: 10.1002/cctc.201900552

Regulating C–C coupling in thermocatalytic and electrocatalytic CO x conversion based on surface science
journal, January 2019

  • Jiang, Yawen; Long, Ran; Xiong, Yujie
  • Chemical Science, Vol. 10, Issue 31
  • DOI: 10.1039/c9sc02014d

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journal, June 2019

  • Sebastián‐Pascual, Paula; Mezzavilla, Stefano; Stephens, Ifan E. L.
  • ChemCatChem, Vol. 11, Issue 16
  • DOI: 10.1002/cctc.201900552

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journal, January 2019

  • Jiang, Yawen; Long, Ran; Xiong, Yujie
  • Chemical Science, Vol. 10, Issue 31
  • DOI: 10.1039/c9sc02014d

A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction
journal, October 2018

  • Lv, Jing-Jing; Jouny, Matthew; Luc, Wesley
  • Advanced Materials, Vol. 30, Issue 49
  • DOI: 10.1002/adma.201803111

Emerging Carbon‐Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value‐Added Chemicals
journal, December 2018


Toward Computational Design of Catalysts for CO 2 Selective Reduction via Reaction Phase Diagram Analysis
journal, January 2019

  • Han, Mengru; Fu, Xiaoyan; Cao, Ang
  • Advanced Theory and Simulations, Vol. 2, Issue 3
  • DOI: 10.1002/adts.201800200

Electrocatalytic Reduction of Gaseous CO 2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes
journal, July 2019


A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
journal, November 2019

  • Daiyan, Rahman; Saputera, Wibawa Hendra; Masood, Hassan
  • Advanced Energy Materials, Vol. 10, Issue 11
  • DOI: 10.1002/aenm.201902106

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO 2 Reduction to Formate
journal, November 2019


Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO 2 Reduction
journal, August 2019


Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels
journal, September 2019


Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide
journal, December 2019


Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO 2 Reduction
journal, September 2019

  • Wang, Jiong; Huang, Xiang; Xi, Shibo
  • Angewandte Chemie International Edition, Vol. 58, Issue 38
  • DOI: 10.1002/anie.201906475

Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels
journal, September 2019

  • Ren, Dan; Gao, Jing; Pan, Linfeng
  • Angewandte Chemie International Edition, Vol. 58, Issue 42
  • DOI: 10.1002/anie.201909610

Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide
journal, December 2019

  • Chen, Ruixue; Su, Hai‐Yan; Liu, Deyu
  • Angewandte Chemie International Edition, Vol. 59, Issue 1
  • DOI: 10.1002/anie.201910662

Changing the Product Selectivity for Electrocatalysis of CO 2 Reduction Reaction on Plated Cu Electrodes
journal, October 2019


Electrochemical Carbon Dioxide Splitting
journal, February 2019


Reactivity Determinants in Electrodeposited Cu Foams for Electrochemical CO 2 Reduction
journal, August 2018

  • Klingan, Katharina; Kottakkat, Tintula; Jovanov, Zarko P.
  • ChemSusChem, Vol. 11, Issue 19
  • DOI: 10.1002/cssc.201801582

Nanostructured Copper-Based Electrocatalysts for CO 2 Reduction
journal, July 2018


Electrochemical Scanning Probe Microscopies in Electrocatalysis
journal, November 2018

  • Liang, Yunchang; Pfisterer, Jonas H. K.; McLaughlin, David
  • Small Methods, Vol. 3, Issue 8
  • DOI: 10.1002/smtd.201800387

Review of two‐dimensional materials for electrochemical CO 2 reduction from a theoretical perspective
journal, April 2019

  • Zhu, Xiaorong; Li, Yafei
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6
  • DOI: 10.1002/wcms.1416

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals
journal, August 2019

  • Basdogan, Yasemin; Maldonado, Alex M.; Keith, John A.
  • WIREs Computational Molecular Science, Vol. 10, Issue 2
  • DOI: 10.1002/wcms.1446

Surface Reconstruction of Polycrystalline Cu Electrodes in Aqueous KHCO3 Electrolyte at Potentials in the Early Stages of CO2 Reduction
journal, April 2018


Bimetallic Electrocatalysts for CO2 Reduction
journal, October 2018

  • Zhu, Wenlei; Tackett, Brian M.; Chen, Jingguang G.
  • Topics in Current Chemistry, Vol. 376, Issue 6
  • DOI: 10.1007/s41061-018-0220-5

Copper adparticle enabled selective electrosynthesis of n-propanol
journal, November 2018


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane
journal, July 2019


Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
journal, August 2019


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

High-rate electroreduction of carbon monoxide to multi-carbon products
journal, August 2018


Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction
journal, December 2018


Carbon monoxide electroreduction as an emerging platform for carbon utilization
journal, December 2019


Establishing new scaling relations on two-dimensional MXenes for CO 2 electroreduction
journal, January 2018

  • Handoko, Albertus D.; Khoo, Khoong Hong; Tan, Teck Leong
  • Journal of Materials Chemistry A, Vol. 6, Issue 44
  • DOI: 10.1039/c8ta06567e

Metal-free graphdiyne doped with sp-hybridized boron and nitrogen atoms at acetylenic sites for high-efficiency electroreduction of CO 2 to CH 4 and C 2 H 4
journal, January 2019

  • Zhao, Jia; Chen, Zhe; Zhao, Jingxiang
  • Journal of Materials Chemistry A, Vol. 7, Issue 8
  • DOI: 10.1039/c8ta11825f

Mechanism and kinetics for both thermal and electrochemical reduction of N 2 catalysed by Ru(0001) based on quantum mechanics
journal, January 2019

  • Chen, Liang-Yu; Kuo, Tung-Chun; Hong, Zih-Siang
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 32
  • DOI: 10.1039/c9cp03187a

Electrochemical CO 2 reduction on Cu and Au electrodes studied using in situ sum frequency generation spectroscopy
journal, January 2019

  • Huang-fu, Zhi-Chao; Song, Qian-Tong; He, Yu-Han
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 45
  • DOI: 10.1039/c9cp04346b

Surface strategies for catalytic CO 2 reduction: from two-dimensional materials to nanoclusters to single atoms
journal, January 2019

  • Wang, Liming; Chen, Wenlong; Zhang, Doudou
  • Chemical Society Reviews, Vol. 48, Issue 21
  • DOI: 10.1039/c9cs00163h

Silicon-doped graphene edges: an efficient metal-free catalyst for the reduction of CO 2 into methanol and ethanol
journal, January 2019

  • Mao, Xin; Kour, Gurpreet; Zhang, Lei
  • Catalysis Science & Technology, Vol. 9, Issue 23
  • DOI: 10.1039/c9cy01709g

Mononuclear Fe in N-doped carbon: computational elucidation of active sites for electrochemical oxygen reduction and oxygen evolution reactions
journal, January 2020

  • Shang, Rui; Steinmann, Stephan N.; Xu, Bo-Qing
  • Catalysis Science & Technology, Vol. 10, Issue 4
  • DOI: 10.1039/c9cy01935a

Reduction of carbon dioxide on photoexcited nanoparticles of VIII group metals
journal, January 2019


Photodriven CO dimerization on Cu 2 O from an electronic-structure perspective
journal, January 2020

  • Hedström, Svante; Halldin Stenlid, Joakim; Liu, Chang
  • Sustainable Energy & Fuels, Vol. 4, Issue 2
  • DOI: 10.1039/c9se00753a

Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials
journal, January 2020

  • Garg, Sahil; Li, Mengran; Weber, Adam Z.
  • Journal of Materials Chemistry A, Vol. 8, Issue 4
  • DOI: 10.1039/c9ta13298h

Selective reduction of CO to acetaldehyde with CuAg electrocatalysts
journal, January 2020

  • Wang, Lei; Higgins, Drew C.; Ji, Yongfei
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 23
  • DOI: 10.1073/pnas.1821683117

Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics
journal, March 2019

  • Cheng, Tao; Fortunelli, Alessandro; Goddard, William A.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 16
  • DOI: 10.1073/pnas.1821709116

Heterogeneous catalysts for catalytic CO2 conversion into value-added chemicals
journal, March 2019


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