Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
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We have carried out a periodic Kohn-Sham density functional theory investigation of the pathways by which carbon-carbon bonds could be formed during the electrochemical reduction of CO2 on Cu(100) using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson-Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C-C bond formation revealed that at low-applied potential, C-C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C-C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C-C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions.
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Later studies revealed inaccuracies in calculating reaction energies in the vacuum approach resulting from the omission of electric field and solvation effects during the simulation.
“However, later studies revealed inaccuracies in calculating reaction energies in this approach.[34-37][38] resulting from the omission of electric field and solvation effects during the simulation.”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [34]
Several microkinetic models on Ag and Cu have been proposed.
“Several microkinetic models on Ag [69] and Cu [34] have been proposed”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [34]
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Cites
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A., & Hennig, R. G. (2014) · The Journal of Chemical Physics · doi:10.1063/1.4865107 · Cited by 3,196 · see citing works
Terrestrial Gross Carbon Dioxide Uptake: Global Distribution and Covariation with Climate
Beer, C., Reichstein, M., Tomelleri, E., Ciais, P., Jung, M., Carvalhais, N., Rödenbeck, C., Arain, M. A., Baldocchi, D., Bonan, G. B., et al. (2010) · Science · doi:10.1126/science.1184984 · Cited by 2,841 · see citing works
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
Kortlever, R., Shen, J., Schouten, K. J. P., Calle‐Vallejo, F., & Koper, M. T. M. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b01559 · Cited by 2,183 · see citing works
Electrochemical CO2 Reduction on Metal Electrodes
Hori, Y. (2008) · Springer eBooks · doi:10.1007/978-0-387-49489-0_3 · Cited by 1,904 · see citing works
Hori, Y., Kikuchi, K., & Suzuki, S. (1985) · Chemistry Letters · doi:10.1246/cl.1985.1695 · Cited by 1,401 · see citing works
Calle‐Vallejo, F., & Koper, M. T. M. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201301470 · Cited by 941 · see citing works
Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
Nie, X., Esopi, M. R., Janik, M. J., & Asthagiri, A. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201208320 · Cited by 928 · see citing works
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis
Koper, M. T. M. (2013) · Chemical Science · doi:10.1039/c3sc50205h · Cited by 908 · see citing works
Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes
Schouten, K. J. P., Qin, Z., Pérez‐Gallent, E., & Koper, M. T. M. (2012) · Journal of the American Chemical Society · doi:10.1021/ja302668n · Cited by 898 · see citing works
Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
Montoya, J. H., Shi, C., Chan, K., & Nørskov, J. K. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b00722 · Cited by 861 · see citing works
Xiao, H. Y., Cheng, T., Goddard, W. A., & Sundararaman, R. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b11390 · Cited by 527 · see citing works
Insights into CC Coupling in CO 2 Electroreduction on Copper Electrodes
Montoya, J. H., Peterson, A. A., & Nørskov, J. K. (2013) · ChemCatChem · doi:10.1002/cctc.201200564 · Cited by 435 · see citing works
The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes
Schouten, K. J. P., Pérez‐Gallent, E., & Koper, M. T. M. (2013) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2013.08.033 · Cited by 402 · see citing works
Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals
Schouten, K. J. P., Gallent, E. P., & Koper, M. T. M. (2013) · ACS Catalysis · doi:10.1021/cs4002404 · Cited by 367 · see citing works
Letchworth-Weaver, K., & Arias, T. A. (2012) · Physical Review B · doi:10.1103/physrevb.86.075140 · Cited by 351 · see citing works
Jinnouchi, R., & Anderson, A. B. (2008) · Physical Review B · doi:10.1103/physrevb.77.245417 · Cited by 319 · see citing works
Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper
Fishman, M., Zhuang, H. L., Mathew, K., et al. (2013) · Physical Review B · doi:10.1103/physrevb.87.245402 · Cited by 295 · see citing works
Cheng, T., Xiao, H. Y., & Goddard, W. A. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b02247 · Cited by 278 · see citing works
Gunceler, D., Letchworth‐Weaver, K., Sundararaman, R., Schwarz, K., & Arias, T. A. (2013) · Modelling and Simulation in Materials Science and Engineering · doi:10.1088/0965-0393/21/7/074005 · Cited by 223 · see citing works
Aqueous and Surface Redox Potentials from Self-Consistently Determined Gibbs Energies
Jinnouchi, R., & Anderson, A. B. (2008) · The Journal of Physical Chemistry C · doi:10.1021/jp802627s · Cited by 152 · see citing works
Alkali cation specific adsorption onto fcc(111) transition metal electrodes
Mills, J. N., McCrum, I. T., & Janik, M. J. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c4cp00760c · Cited by 120 · see citing works
First-principles based microkinetic modeling of borohydride oxidation on a Au(111) electrode
Rostamikia, G., Mendoza, A. J., Hickner, M. A., & Janik, M. J. (2011) · Journal of Power Sources · doi:10.1016/j.jpowsour.2011.07.042 · Cited by 101 · see citing works
The electrochemical characterization of copper single-crystal electrodes in alkaline media
Schouten, K. J. P., Gallent, E. P., & Koper, M. T. M. (2013) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2013.03.018 · Cited by 95 · see citing works
Joint density-functional theory for electronic structure of solvated systems
Petrosyan, S., Briere, J.-F., Roundy, D. J., & Arias, T. A. (2007) · Physical Review B · doi:10.1103/physrevb.75.205105 · Cited by 94 · see citing works
Koga, O., Watanabe, Y., Tanizaki, M., et al. (2001) · Electrochimica Acta · doi:10.1016/s0013-4686(01)00599-0 · Cited by 39 · see citing works
Specific adsorption of fluoride ions on the (110) face of a silver single crystal electrode
Bacchetta, M. D., Trasatti, S. P. M., Doubova, L., et al. (1988) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(88)80017-2 · Cited by 24 · see citing works
Ou, L., Long, W., Chen, Y., & Jin, J. (2015) · RSC Advances · doi:10.1039/c5ra15905a · Cited by 21 · see citing works
Flagged first, then by citations
Research works printed but not linked: 5
- Ou, L.; Long, W.; Chen, Y.; Jin, J. RSC Adv. 2015, 5, 96281- 96289.
- Montoya, J. H.; Peterson, A. A.; Nørskov, J. K. Insights into C-C Coupling in CO2Electroreduction on Copper Electrodes. Chem- CatChem 2013, 5 (3), 737-742.
- Fishman, M.; Zhuang, H. L.; Mathew, K.; Dirschka, W.; Hennig, R. G. Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper. Phys. Rev. B: Condens. Matter Mater. Phys. 2013, 87 (24), 245402.
- Modern Aspects of Electrochemistry; Springer US: New York, 1999; p 644.
- Hori, Y.; Kikuchi, K.; Suzuki, S. Production of CO and CH 4 in electrochemical reduction of CO 2 at Metal Electrodues in Aqeous Hydrogencarbonate Solution. Chem. Lett. 1985, 14 (11), 1695-1698.
Cited by
Sorted by citations
Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte
Nitopi, S., Bertheussen, E., Scott, S. B., Liu, X., Engstfeld, A. K., Horch, S., Seger, B., Stephens, I. E. L., Chan, K., Hahn, C., et al. (2019) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00705 · Cited by 5,223 · see citing works
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
Birdja, Y. Y., Pérez-Gallent, E., Figueiredo, M. C., Göttle, A. J., Calle-Vallejo, F., & Koper, M. T. M. (2019) · Nature Energy · doi:10.1038/s41560-019-0450-y · Cited by 2,747 · see citing works
Dinh, C.-T., Burdyny, T., Kibria, M. G., Seifitokaldani, A., Gabardo, C. M., García de Arquer, F. P., Kiani, A., Edwards, J. P., De Luna, P., Bushuyev, O. S., et al. (2018) · Science · doi:10.1126/science.aas9100 · Cited by 2,515 · see citing works
What Should We Make with CO2 and How Can We Make It?
Bushuyev, O. S., De Luna, P., Dinh, C. T., Tao, L., Saur, G., van de Lagemaat, J., Kelley, S. O., & Sargent, E. H. (2018) · Joule · doi:10.1016/j.joule.2017.09.003 · Cited by 1,593 · see citing works
Kibria, M. G., Edwards, J. P., Gabardo, C. M., Dinh, C., Seifitokaldani, A., Sinton, D., & Sargent, E. H. (2019) · Advanced Materials · doi:10.1002/adma.201807166 · Cited by 1,331 · see citing works
Designing materials for electrochemical carbon dioxide recycling
Ross, M. B., De Luna, P., Li, Y., Dinh, C.-T., Kim, D., Yang, P., & Sargent, E. H. (2019) · Nature Catalysis · doi:10.1038/s41929-019-0306-7 · Cited by 1,302 · see citing works
Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons
Zhou, Y., Che, F., Liu, M., Zou, C., Liang, Z., De Luna, P., Yuan, H., Li, J., Wang, Z., Xie, H., et al. (2018) · Nature Chemistry · doi:10.1038/s41557-018-0092-x · Cited by 1,171 · see citing works
Electric Field Effects in Electrochemical CO <sub>2</sub> Reduction
Chen, L. D., Urushihara, M., Chan, K., & Nørskov, J. K. (2016) · ACS Catalysis · doi:10.1021/acscatal.6b02299 · Cited by 702 · see citing works
Theoretical Insights into Heterogeneous (Photo)electrochemical CO<sub>2</sub>Reduction
Xu, S., & Carter, E. A. (2019) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00481 · Cited by 652 · see citing works
Xiao, H., Cheng, T., & Goddard, W. A. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b06846 · Cited by 458 · see citing works
Cheng, T., Xiao, H., & Goddard, W. A. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b08534 · Cited by 453 · see citing works
Lum, Y., & Ager, J. W. (2018) · Nature Catalysis · doi:10.1038/s41929-018-0201-7 · Cited by 322 · see citing works
Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
Lum, Y., Cheng, T., Goddard, W. A., & Ager, J. W. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.8b03986 · Cited by 251 · see citing works
Effects of Anion Identity and Concentration on Electrochemical Reduction of CO <sub>2</sub>
Resasco, J., Lum, Y., Clark, E., Zeledon, J. Z., & Bell, A. T. (2018) · ChemElectroChem · doi:10.1002/celc.201701316 · Cited by 250 · see citing works
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Miao, L., Jia, W., Cao, X., & Jiao, L. (2024) · Chemical Society Reviews · doi:10.1039/d2cs01068b · Cited by 241 · see citing works
Role of oxygen-bound reaction intermediates in selective electrochemical CO <sub>2</sub> reduction
Zhi, X., Vasileff, A., Zheng, Y., Jiao, Y., & Qiao, S.-Z. (2021) · Energy & Environmental Science · doi:10.1039/d1ee00740h · Cited by 149 · see citing works
Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO <sub>2</sub> on Copper?
Garza, A. J., Bell, A. T., & Head-Gordon, M. (2018) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.7b03180 · Cited by 148 · see citing works
Self-citationMarepally, B. C., Ampelli, C., Genovese, C., Saboo, T., Perathoner, S., Wisser, F. M., Veyre, L., Canivet, J., Quadrelli, E. A., & Centi, G. (2017) · ChemSusChem · doi:10.1002/cssc.201701506 · Cited by 62 · see citing works
- Authors
- Goodpaster, J. D., Bell, A. T., & Head-Gordon, M.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- University of California, Berkeley (US)
- Department of Chemistry, University of California at Berkeley, Berkeley, California 94720, United States
- Corresponding author
- Bell, Alexis T.
- Venue
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-04-07
- Volume
- 7
- Issue
- 8
- Pages
- 1471-1477
- ISSN
- 1948-7185 (ISSN-L)
- OpenAlex
- W2313201239
- Cited by
- 702
- References
- 27
- Citations by year
- 2026: 56 · 2025: 80 · 2024: 110 · 2023: 92 · 2022: 82 · 2021: 100 · 2020: 56 · 2019: 50 · 2018: 44 · 2017: 25 · 2016: 7
- FWCI
- 11.41
- Type
- journal article
- Language
- en
- Open access
- green
- escholarship.org
- Locations
- The Journal of Physical Chemistry Letters (publishedVersion)
- PubMed (publishedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- Funders
- Office of Science (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
- electrochemical CO2 reduction, C–C bond formation, ethene formation, Cu(100) surface, CO dimer, reaction mechanism, activation barrier, microkinetic model, potential of zero charge, electrochemical potential, solvent effects, reaction kinetics
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