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Title: Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2

Abstract

The electrochemical reduction of CO2 is known to be influenced by the concentration and identity of the anionic species in the electrolyte; however, a full understanding of this phenomenon has not been developed. Here, we present the results of experimental and computational studies aimed at understanding the role of electrolyte anions on the reduction of CO2 over Cu surfaces. Experimental studies were performed to show the effects of bicarbonate buffer concentration and the composition of other buffering anions on the partial currents of the major products formed by reduction of CO2 over Cu. It was demonstrated that the composition and concentration of electrolyte anions has relatively little effect on the formation of CO, HCOO-, C2H4, and CH3CH2OH, but has a significant effect on the formation of H2 and CH4. Continuum modeling was used to assess the effects of buffering anions on the pH at the electrode surface. The influence of pH on the activity of Cu for producing H2 and CH4 was also considered. Changes in the pH near the electrode surface were insufficient to explain the differences in activity and selectivity observed with changes in anion buffering capacity observed for the formation of H2 and CH4. Therefore, it ismore » proposed that these differences are the result of the ability of buffering anions to donate hydrogen directly to the electrode surface and in competition with water. The effectiveness of buffering anions to serve as hydrogen donors is found to increase with decreasing pKa of the buffering anion.« less

Authors:
 [1];  [2];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1571098
Alternate Identifier(s):
OSTI ID: 1420191
Grant/Contract Number:  
AC02-05CH11231; SC0004993; DGE-0802270
Resource Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 5; Journal Issue: 7; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, and Bell, Alexis T. Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2. United States: N. p., 2018. Web. doi:10.1002/celc.201701316.
Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, & Bell, Alexis T. Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2. United States. https://doi.org/10.1002/celc.201701316
Resasco, Joaquin, Lum, Yanwei, Clark, Ezra, Zeledon, Jose Zamora, and Bell, Alexis T. Mon . "Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2". United States. https://doi.org/10.1002/celc.201701316. https://www.osti.gov/servlets/purl/1571098.
@article{osti_1571098,
title = {Effects of Anion Identity and Concentration on Electrochemical Reduction of CO2},
author = {Resasco, Joaquin and Lum, Yanwei and Clark, Ezra and Zeledon, Jose Zamora and Bell, Alexis T.},
abstractNote = {The electrochemical reduction of CO2 is known to be influenced by the concentration and identity of the anionic species in the electrolyte; however, a full understanding of this phenomenon has not been developed. Here, we present the results of experimental and computational studies aimed at understanding the role of electrolyte anions on the reduction of CO2 over Cu surfaces. Experimental studies were performed to show the effects of bicarbonate buffer concentration and the composition of other buffering anions on the partial currents of the major products formed by reduction of CO2 over Cu. It was demonstrated that the composition and concentration of electrolyte anions has relatively little effect on the formation of CO, HCOO-, C2H4, and CH3CH2OH, but has a significant effect on the formation of H2 and CH4. Continuum modeling was used to assess the effects of buffering anions on the pH at the electrode surface. The influence of pH on the activity of Cu for producing H2 and CH4 was also considered. Changes in the pH near the electrode surface were insufficient to explain the differences in activity and selectivity observed with changes in anion buffering capacity observed for the formation of H2 and CH4. Therefore, it is proposed that these differences are the result of the ability of buffering anions to donate hydrogen directly to the electrode surface and in competition with water. The effectiveness of buffering anions to serve as hydrogen donors is found to increase with decreasing pKa of the buffering anion.},
doi = {10.1002/celc.201701316},
journal = {ChemElectroChem},
number = 7,
volume = 5,
place = {United States},
year = {Mon Feb 12 00:00:00 EST 2018},
month = {Mon Feb 12 00:00:00 EST 2018}
}

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Works referenced in this record:

Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016

  • Goodpaster, Jason D.; Bell, Alexis T.; Head-Gordon, Martin
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 8
  • DOI: 10.1021/acs.jpclett.6b00358

Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes
journal, March 2017

  • Ledezma-Yanez, Isis; Wallace, W. David Z.; Sebastián-Pascual, Paula
  • Nature Energy, Vol. 2, Issue 4
  • DOI: 10.1038/nenergy.2017.31

Potential of zero charge of monocrystalline copper electrodes in perchlorate solutions
journal, June 2004


Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

Modeling CO2 reduction on Pt(111)
journal, January 2013

  • Shi, Chuan; O'Grady, Christopher P.; Peterson, Andrew A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 19
  • DOI: 10.1039/c3cp50645b

Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008


Electrochemical Reduction of CO at a Copper Electrode
journal, September 1997

  • Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru
  • The Journal of Physical Chemistry B, Vol. 101, Issue 36
  • DOI: 10.1021/jp970284i

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts
journal, January 2016

  • Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/C6CP05287H

New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014

  • Durst, J.; Siebel, A.; Simon, C.
  • Energy Environ. Sci., Vol. 7, Issue 7
  • DOI: 10.1039/C4EE00440J

Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media
journal, August 1994

  • Hori, Yoshio; Wakebe, Hidetoshi; Tsukamoto, Toshio
  • Electrochimica Acta, Vol. 39, Issue 11-12, p. 1833-1839
  • DOI: 10.1016/0013-4686(94)85172-7

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
  • DOI: 10.1021/jacs.6b13287

Direct Observation on Reaction Intermediates and the Role of Bicarbonate Anions in CO 2 Electrochemical Reduction Reaction on Cu Surfaces
journal, October 2017

  • Zhu, Shangqian; Jiang, Bei; Cai, Wen-Bin
  • Journal of the American Chemical Society, Vol. 139, Issue 44
  • DOI: 10.1021/jacs.7b10462

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015

  • Sheng, Wenchao; Zhuang, Zhongbin; Gao, Minrui
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6848

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
  • DOI: 10.1073/pnas.1602984113

Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO 2 Electroreduction by Process Conditions
journal, December 2014


The Mechanism of the Cathodic Hydrogen Evolution Reaction
journal, January 1952

  • Bockris, J. O'M.; Potter, E. C.
  • Journal of The Electrochemical Society, Vol. 99, Issue 4
  • DOI: 10.1149/1.2779692

Engineering Cu surfaces for the electrocatalytic conversion of CO 2 : Controlling selectivity toward oxygenates and hydrocarbons
journal, May 2017

  • Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 23
  • DOI: 10.1073/pnas.1618935114

Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014

  • Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja505791r

The Evolution of the Polycrystalline Copper Surface, First to Cu(111) and Then to Cu(100), at a Fixed CO 2 RR Potential: A Study by Operando EC-STM
journal, December 2014

  • Kim, Youn-Geun; Baricuatro, Jack Hess; Javier, Alnald
  • Langmuir, Vol. 30, Issue 50
  • DOI: 10.1021/la504445g

Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
  • DOI: 10.1073/pnas.1612106114

Electrolytic Reduction of Carbon Dioxide at Mercury Electrode in Aqueous Solution
journal, March 1982

  • Hori, Yoshio; Suzuki, Shin
  • Bulletin of the Chemical Society of Japan, Vol. 55, Issue 3
  • DOI: 10.1246/bcsj.55.660

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
  • DOI: 10.1007/s10800-005-9058-y

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction
journal, June 2017

  • Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter
  • The Journal of Physical Chemistry C, Vol. 121, Issue 26
  • DOI: 10.1021/acs.jpcc.7b03673

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water
journal, October 2016

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08534

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

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
  • DOI: 10.1021/jacs.7b06765

Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide
journal, January 2015

  • Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 29
  • DOI: 10.1039/C5CP03283K

Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

Opportunities and challenges for a sustainable energy future
journal, August 2012

  • Chu, Steven; Majumdar, Arun
  • Nature, Vol. 488, Issue 7411, p. 294-303
  • DOI: 10.1038/nature11475

Determination of the rate constants for the carbon dioxide to bicarbonate inter-conversion in pH-buffered seawater systems
journal, June 2006


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
  • DOI: 10.1039/c2ee21234j

Bicarbonate Is Not a General Acid in Au-Catalyzed CO 2 Electroreduction
journal, November 2017

  • Wuttig, Anna; Yoon, Youngmin; Ryu, Jaeyune
  • Journal of the American Chemical Society, Vol. 139, Issue 47
  • DOI: 10.1021/jacs.7b08345

Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017

  • Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15438

Thermodynamic Studies of Anion Adsorption at Stepped Platinum( h kl ) Electrode Surfaces in Sulfuric Acid Solutions
journal, December 2002

  • Mostany, Jorge; Herrero, Enrique; Feliu, Juan M.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 49
  • DOI: 10.1021/jp026561p

Epitaxial growth of Cu on Si by magnetron sputtering
journal, November 1998

  • Jiang, H.; Klemmer, T. J.; Barnard, J. A.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 16, Issue 6
  • DOI: 10.1116/1.581489

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
  • DOI: 10.1021/ja309317u

Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
journal, May 2015

  • Montoya, Joseph H.; Shi, Chuan; Chan, Karen
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 11
  • DOI: 10.1021/acs.jpclett.5b00722

CRC Handbook of Chemistry and Physics
book, June 2014


Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption
journal, February 2013

  • Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1574

Works referencing / citing this record:

Interplay of Homogeneous Reactions, Mass Transport, and Kinetics in Determining Selectivity of the Reduction of CO 2 on Gold Electrodes
journal, June 2019


In Situ Infrared Spectroscopy Reveals Persistent Alkalinity near Electrode Surfaces during CO 2 Electroreduction
journal, September 2019

  • Yang, Kailun; Kas, Recep; Smith, Wilson A.
  • Journal of the American Chemical Society, Vol. 141, Issue 40
  • DOI: 10.1021/jacs.9b07000

Competition between CO 2 Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions
journal, February 2020

  • Goyal, Akansha; Marcandalli, Giulia; Mints, Vladislav A.
  • Journal of the American Chemical Society, Vol. 142, Issue 9
  • DOI: 10.1021/jacs.9b10061

CO2 Electroreduction in Ionic Liquids
journal, March 2019

  • Faggion, Deonildo; Gonçalves, Wellington D. G.; Dupont, Jairton
  • Frontiers in Chemistry, Vol. 7
  • DOI: 10.3389/fchem.2019.00102