Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold
Abstract
Electrochemical CO2 reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO2 reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO2 adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO2 adsorption at intermediate ones, and CO2 mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO2 and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.
- Authors:
-
- Stanford Univ., Stanford, CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- Stanford Univ., Stanford, CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Univ. of California, Los Angeles, CA (United States). Dept. of Chemical and Biomolecular Engineering
- California Inst. of Technology (CalTech), Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering
- Technical Univ. of Denmark, Lyngby (Denmark). CatTheory Center, Dept. of Physics
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); Swiss National Science Foundation (SNSF)
- OSTI Identifier:
- 1575240
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, and Chan, Karen. Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold. United States: N. p., 2020.
Web. doi:10.1038/s41467-019-13777-z.
Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, & Chan, Karen. Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold. United States. https://doi.org/10.1038/s41467-019-13777-z
Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, and Chan, Karen. Tue .
"Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold". United States. https://doi.org/10.1038/s41467-019-13777-z. https://www.osti.gov/servlets/purl/1575240.
@article{osti_1575240,
title = {Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold},
author = {Ringe, Stefan and Morales-Guio, Carlos G. and Chen, Leanne D. and Fields, Meredith and Jaramillo, Thomas F. and Hahn, Christopher and Chan, Karen},
abstractNote = {Electrochemical CO2 reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO2 reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO2 adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO2 adsorption at intermediate ones, and CO2 mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO2 and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.},
doi = {10.1038/s41467-019-13777-z},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 6 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Global Optimization of Adsorbate–Surface Structures While Preserving Molecular Identity
journal, October 2013
- Peterson, Andrew A.
- Topics in Catalysis, Vol. 57, Issue 1-4
Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products
journal, July 2018
- Wang, Lei; Nitopi, Stephanie A.; Bertheussen, Erlend
- ACS Catalysis, Vol. 8, Issue 8
A Pore-Scale Model of Oxygen Reduction in Ionomer-Free Catalyst Layers of PEFCs
journal, January 2011
- Chan, Karen; Eikerling, Michael
- Journal of The Electrochemical Society, Vol. 158, Issue 1
Electrochemical reduction of carbon dioxides to carbon monoxide at a gold electrode in aqueous potassium hydrogen carbonate
journal, January 1987
- Hori, Yoshio; Murata, Akira; Kikuchi, Katsuhei
- Journal of the Chemical Society, Chemical Communications, Issue 10
Tuning of CO 2 Reduction Selectivity on Metal Electrocatalysts
journal, September 2017
- Wang, Yuhang; Liu, Junlang; Wang, Yifei
- Small, Vol. 13, Issue 43
CO-CO coupling on Cu facets: Coverage, strain and field effects
journal, December 2016
- Sandberg, Robert B.; Montoya, Joseph H.; Chan, Karen
- Surface Science, Vol. 654
The metal-liquid electrolyte interface
journal, February 1997
- Parsons, R.
- Solid State Ionics, Vol. 94, Issue 1-4
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO 2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates
journal, December 2018
- Katayama, Yu; Nattino, Francesco; Giordano, Livia
- The Journal of Physical Chemistry C, Vol. 123, Issue 10
Theoretical Approaches to Describing the Oxygen Reduction Reaction Activity of Single-Atom Catalysts
journal, November 2018
- Patel, Anjli M.; Ringe, Stefan; Siahrostami, Samira
- The Journal of Physical Chemistry C, Vol. 122, Issue 51
Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory
journal, June 2008
- Jinnouchi, Ryosuke; Anderson, Alfred B.
- Physical Review B, Vol. 77, Issue 24
Facile Electron Transfer to CO 2 during Adsorption at the Metal|Solution Interface
journal, November 2019
- Gauthier, Joseph A.; Fields, Meredith; Bajdich, Michal
- The Journal of Physical Chemistry C, Vol. 123, Issue 48
Potential Dependence of Electrochemical Barriers from ab Initio Calculations
journal, April 2016
- Chan, Karen; Nørskov, Jens K.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
Adsorption of large ions from an electrolyte solution: a modified Poisson–Boltzmann equation
journal, November 2000
- Borukhov, I.; Andelman, D.; Orland, H.
- Electrochimica Acta, Vol. 46, Issue 2-3
Understanding cation effects in electrochemical CO 2 reduction
journal, January 2019
- Ringe, Stefan; Clark, Ezra L.; Resasco, Joaquin
- Energy & Environmental Science, Vol. 12, Issue 10
The structure of the electrochemical double layer: Ag(111) in alkaline electrolyte
journal, November 2011
- Lucas, Christopher A.; Thompson, Paul; Gründer, Yvonne
- Electrochemistry Communications, Vol. 13, Issue 11
Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
journal, January 2014
- Shi, Chuan; Hansen, Heine A.; Lausche, Adam C.
- Physical Chemistry Chemical Physics, Vol. 16, Issue 10
Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide
journal, August 2017
- Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra
- Journal of the American Chemical Society, Vol. 139, Issue 32
Understanding Surface-Mediated Electrochemical Reactions: CO 2 Reduction and Beyond
journal, July 2018
- Dunwell, Marco; Luc, Wesley; Yan, Yushan
- ACS Catalysis, Vol. 8, Issue 9
pH Effects on the Selectivity of the Electrocatalytic CO 2 Reduction on Graphene-Embedded Fe–N–C Motifs: Bridging Concepts between Molecular Homogeneous and Solid-State Heterogeneous Catalysis
journal, March 2018
- Varela, Ana Sofia; Kroschel, Matthias; Leonard, Nathaniel D.
- ACS Energy Letters, Vol. 3, Issue 4
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH
journal, February 2016
- Varela, Ana Sofia; Kroschel, Matthias; Reier, Tobias
- Catalysis Today, Vol. 260
Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models
journal, October 2017
- Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 42
Optimizing mesostructured silver catalysts for selective carbon dioxide conversion into fuels
journal, January 2019
- Suter, Silvan; Haussener, Sophia
- Energy & Environmental Science, Vol. 12, Issue 5
Interplay of Homogeneous Reactions, Mass Transport, and Kinetics in Determining Selectivity of the Reduction of CO 2 on Gold Electrodes
journal, June 2019
- Zhang, Benjamin A.; Ozel, Tuncay; Elias, Joseph S.
- ACS Central Science, Vol. 5, Issue 6
First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006
- Otani, M.; Sugino, O.
- Physical Review B, Vol. 73, Issue 11
Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction
journal, July 2018
- Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh
- Angewandte Chemie International Edition, Vol. 57, Issue 30
Impedance studies of reconstructed and non-reconstructed gold single crystal surfaces
journal, December 1996
- Eberhardt, D.; Santos, E.; Schmickler, W.
- Journal of Electroanalytical Chemistry, Vol. 419, Issue 1
A Two-Dimensional MoS 2 Catalysis Transistor by Solid-State Ion Gating Manipulation and Adjustment (SIGMA)
journal, September 2019
- Wu, Yecun; Ringe, Stefan; Wu, Chun-Lan
- Nano Letters, Vol. 19, Issue 10
Simulations of Cyclic Voltammetry for Electric Double Layers in Asymmetric Electrolytes: A Generalized Modified Poisson–Nernst–Planck Model
journal, August 2013
- Wang, Hainan; Thiele, Alexander; Pilon, Laurent
- The Journal of Physical Chemistry C, Vol. 117, Issue 36
Ab initio molecular dynamics study of the Helmholtz layer formed on solid–liquid interfaces and its capacitance
journal, January 2013
- Ando, Yasunobu; Gohda, Yoshihiro; Tsuneyuki, Shinji
- Chemical Physics Letters, Vol. 556
Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO 2 to CO
journal, March 2019
- Clark, Ezra L.; Ringe, Stefan; Tang, Michael
- ACS Catalysis, Vol. 9, Issue 5
Surface Atomic Arrangement Dependence of Electrochemical CO 2 Reduction on Gold: Online Electrochemical Mass Spectrometric Study on Low-Index Au( hkl ) Surfaces
journal, January 2019
- Todoroki, Naoto; Tei, Hiroki; Tsurumaki, Hiroto
- ACS Catalysis, Vol. 9, Issue 2
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst
journal, October 2018
- Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A.
- Nature Catalysis, Vol. 1, Issue 10
Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models
journal, November 2018
- Gauthier, Joseph A.; Ringe, Stefan; Dickens, Colin F.
- ACS Catalysis, Vol. 9, Issue 2
Theory of the voltammetric response of electrodes of submicron dimensions. Violation of electroneutrality in the presence of excess supporting electrolyte
journal, December 1993
- Smith, Christopher P.; White, Henry S.
- Analytical Chemistry, Vol. 65, Issue 23
Selective increase in CO 2 electroreduction activity at grain-boundary surface terminations
journal, November 2017
- Mariano, Ruperto G.; McKelvey, Kim; White, Henry S.
- Science, Vol. 358, Issue 6367
Deuterium isotope effect on the dissociation of weak acids in water and deuterium oxide
journal, May 1969
- Robinson, R. A.; Paabo, Maya; Bates, Roger G.
- Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 73A, Issue 3
The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold
journal, March 2017
- Dunwell, Marco; Lu, Qi; Heyes, Jeffrey M.
- Journal of the American Chemical Society, Vol. 139, Issue 10
Electrochemical CO 2 Reduction: A Classification Problem
journal, October 2017
- Bagger, Alexander; Ju, Wen; Varela, Ana Sofia
- ChemPhysChem, Vol. 18, Issue 22
Inhibited proton transfer enhances Au-catalyzed CO 2 -to-fuels selectivity
journal, July 2016
- Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 32
Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO
journal, January 2013
- Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
Design principles for hydrogen evolution reaction catalyst materials
journal, November 2016
- Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan
- Nano Energy, Vol. 29
Influence of cation adsorption on the kinetics of electrode processes
journal, January 1959
- Frumkin, A. N.
- Transactions of the Faraday Society, Vol. 55
Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016
- Chen, Leanne D.; Urushihara, Makoto; Chan, Karen
- ACS Catalysis, Vol. 6, Issue 10
Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products
journal, January 2017
- Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 24
Electrochemical CO Reduction: A Property of the Electrochemical Interface
journal, December 2018
- Bagger, Alexander; Arnarson, Logi; Hansen, Martin H.
- Journal of the American Chemical Society, Vol. 141, Issue 4
The Relative Reaction Velocities of Isotopic Molecules
journal, August 1949
- Bigeleisen, Jacob
- The Journal of Chemical Physics, Vol. 17, Issue 8
Examination of Near-Electrode Concentration Gradients and Kinetic Impacts on the Electrochemical Reduction of CO 2 using Surface-Enhanced Infrared Spectroscopy
journal, April 2018
- Dunwell, Marco; Yang, Xuan; Setzler, Brian P.
- ACS Catalysis, Vol. 8, Issue 5
The path towards sustainable energy
journal, December 2016
- Chu, Steven; Cui, Yi; Liu, Nian
- Nature Materials, Vol. 16, Issue 1
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016
- Liu, Min; Pang, Yuanjie; Zhang, Bo
- Nature, Vol. 537, Issue 7620
Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions
journal, October 2005
- Gupta, N.; Gattrell, M.; MacDougall, B.
- Journal of Applied Electrochemistry, Vol. 36, Issue 2
Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media
journal, May 2017
- Ooka, Hideshi; Figueiredo, Marta C.; Koper, Marc T. M.
- Langmuir, Vol. 33, Issue 37
Nernst‐Planck Equations and the Electroneutrality and Donnan Equilibrium Assumptions
journal, April 1968
- MacGillivray, A. D.
- The Journal of Chemical Physics, Vol. 48, Issue 7
Revised self-consistent continuum solvation in electronic-structure calculations
journal, February 2012
- Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola
- The Journal of Chemical Physics, Vol. 136, Issue 6
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Current-Voltage Relations for Electrochemical Thin Films
journal, January 2005
- Bazant, Martin Z.; Chu, Kevin T.; Bayly, B. J.
- SIAM Journal on Applied Mathematics, Vol. 65, Issue 5
Barriers of Electrochemical CO 2 Reduction on Transition Metals
journal, July 2016
- Shi, Chuan; Chan, Karen; Yoo, Jong Suk
- Organic Process Research & Development, Vol. 20, Issue 8
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012
- Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
- Energy & Environmental Science, Vol. 5, Issue 5
Proton-Coupled Electron Transfer in Solution, Proteins, and Electrochemistry †
journal, November 2008
- Hammes-Schiffer, Sharon; Soudackov, Alexander V.
- The Journal of Physical Chemistry B, Vol. 112, Issue 45
Electrochemical Capacitance of CO-Terminated Pt(111) Dominated by the CO–Solvent Gap
journal, October 2017
- Sundararaman, Ravishankar; Figueiredo, Marta C.; Koper, Marc T. M.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 21
Imposed currents in galvanic cells
journal, August 2009
- Biesheuvel, P. M.; van Soestbergen, M.; Bazant, M. Z.
- Electrochimica Acta, Vol. 54, Issue 21
Aqueous CO 2 Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles
journal, November 2012
- Chen, Yihong; Li, Christina W.; Kanan, Matthew W.
- Journal of the American Chemical Society, Vol. 134, Issue 49
Unified Approach to Implicit and Explicit Solvent Simulations of Electrochemical Reaction Energetics
journal, October 2019
- Gauthier, Joseph A.; Dickens, Colin F.; Heenen, Hendrik H.
- Journal of Chemical Theory and Computation, Vol. 15, Issue 12
pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019
- Liu, Xinyan; Schlexer, Philomena; Xiao, Jianping
- Nature Communications, Vol. 10, Issue 1
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, June 2009
- Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T.
- Journal of the American Chemical Society, Vol. 131, Issue 23
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, September 2009
- Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T.
- Journal of the American Chemical Society, Vol. 131, Issue 37
Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction
journal, July 2018
- Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh
- Angewandte Chemie, Vol. 130, Issue 30
Electrochemical Capacitance of CO-terminated Pt(111) is Dominated by CO-Solvent Gap
text, January 2017
- Sundararaman, Ravishankar; Figueiredo, Marta C.; Koper, Marc T. M.
- arXiv
An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates
text, January 2019
- Katayama, Yu; Nattino, Francesco; Giordano, Livia
- arXiv