Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu
Abstract
Electrolyte cation size is known to influence the electrochemical reduction of CO2 over metals; however, a satisfactory explanation for this phenomenon has not been developed. In this paper, we report that these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in the vicinity of the cathode. With increasing cation size, the pKa for cation hydrolysis decreases and is sufficiently low for hydrated K+, Rb+, and Cs+ to serve as buffering agents. Buffering lowers the pH near the cathode, leading to an increase in the local concentration of dissolved CO2. Finally, the consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H2 and CH4, and an increase in Faradaic efficiencies for CO, C2H4, and C2H5OH, in full agreement with experimental observations for CO2 reduction over Ag and Cu.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of Chicago, IL (United States). Department of Chemical Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Korea Research Institute of Chemical Technology, Daejeon (Korea). Carbon Resources Institute
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Department of Materials Science & Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Department of Chemical & Biomolecular Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1456958
- Grant/Contract Number:
- AC02-05CH11231; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 39; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., and Bell, Alexis T. Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b07612.
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., & Bell, Alexis T. Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. United States. https://doi.org/10.1021/jacs.6b07612
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., and Bell, Alexis T. Wed .
"Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu". United States. https://doi.org/10.1021/jacs.6b07612. https://www.osti.gov/servlets/purl/1456958.
@article{osti_1456958,
title = {Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu},
author = {Singh, Meenesh R. and Kwon, Youngkook and Lum, Yanwei and Ager, Joel W. and Bell, Alexis T.},
abstractNote = {Electrolyte cation size is known to influence the electrochemical reduction of CO2 over metals; however, a satisfactory explanation for this phenomenon has not been developed. In this paper, we report that these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in the vicinity of the cathode. With increasing cation size, the pKa for cation hydrolysis decreases and is sufficiently low for hydrated K+, Rb+, and Cs+ to serve as buffering agents. Buffering lowers the pH near the cathode, leading to an increase in the local concentration of dissolved CO2. Finally, the consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H2 and CH4, and an increase in Faradaic efficiencies for CO, C2H4, and C2H5OH, in full agreement with experimental observations for CO2 reduction over Ag and Cu.},
doi = {10.1021/jacs.6b07612},
journal = {Journal of the American Chemical Society},
number = 39,
volume = 138,
place = {United States},
year = {Wed Sep 14 00:00:00 EDT 2016},
month = {Wed Sep 14 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
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:
Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels
journal, October 2015
- Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 45
Opportunities and challenges for a sustainable energy future
journal, August 2012
- Chu, Steven; Majumdar, Arun
- Nature, Vol. 488, Issue 7411, p. 294-303
Sustainable hydrocarbon fuels by recycling CO 2 and H 2 O with renewable or nuclear energy
journal, January 2011
- Graves, Christopher; Ebbesen, Sune D.; Mogensen, Mogens
- Renewable and Sustainable Energy Reviews, Vol. 15, Issue 1
Air as the renewable carbon source of the future: an overview of CO2 capture from the atmosphere
journal, January 2012
- Goeppert, Alain; Czaun, Miklos; Surya Prakash, G. K.
- Energy & Environmental Science, Vol. 5, Issue 7
CO2 extraction from seawater using bipolar membrane electrodialysis
journal, January 2012
- Eisaman, Matthew D.; Parajuly, Keshav; Tuganov, Alexander
- Energy & Environmental Science, Vol. 5, Issue 6
Oligomerization of ethene over nickel-exchanged zeolite y into a diesel-range product
journal, September 1988
- Heveling, Josef; van der Beek, Adriaan; de Pender, Marcel
- Applied Catalysis, Vol. 42, Issue 2
Catalysis of the electrochemical reduction of carbon dioxide
journal, January 2013
- Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
- Chem. Soc. Rev., Vol. 42, Issue 6
Insights into the electrocatalytic reduction of CO 2 on metallic silver surfaces
journal, January 2014
- Hatsukade, Toru; Kuhl, Kendra P.; Cave, Etosha R.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 27
Differential Electrochemical Mass Spectrometer Cell Design for Online Quantification of Products Produced during Electrochemical Reduction of CO 2
journal, July 2015
- Clark, Ezra L.; Singh, Meenesh R.; Kwon, Youngkook
- Analytical Chemistry, Vol. 87, Issue 15
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles
journal, September 2014
- Kim, Dohyung; Resasco, Joaquin; Yu, Yi
- Nature Communications, Vol. 5, Issue 1
A selective and efficient electrocatalyst for carbon dioxide reduction
journal, January 2014
- Lu, Qi; Rosen, Jonathan; Zhou, Yang
- Nature Communications, Vol. 5, Issue 1
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014
- Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
- Nature, Vol. 508, Issue 7497
Electrochemical CO 2 and CO Reduction on Metal-Functionalized Porphyrin-like Graphene
journal, April 2013
- Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza
- The Journal of Physical Chemistry C, Vol. 117, Issue 18
Electrochemical reduction of carbon dioxide to ethylene with high Faradaic efficiency at a Cu electrode in CsOH/methanol
journal, September 1999
- Kaneco, Satoshi; Iiba, Kenji; Hiei, Nobu-hide
- Electrochimica Acta, Vol. 44, Issue 26, p. 4701-4706
Ionic liquids enhance the electrochemical CO 2 reduction catalyzed by MoO 2
journal, January 2015
- Oh, Yeonji; Hu, Xile
- Chemical Communications, Vol. 51, Issue 71
Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution
journal, January 1989
- Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 8
Product Selectivity Affected by Cationic Species in Electrochemical Reduction of CO 2 and CO at a Cu Electrode
journal, January 1991
- Murata, Akira; Hori, Yoshio
- Bulletin of the Chemical Society of Japan, Vol. 64, Issue 1
Effect of solution pH on CO: formate formation rates during electrochemical reduction of aqueous CO2 at Sn cathodes
journal, September 2014
- Bumroongsakulsawat, P.; Kelsall, G. H.
- Electrochimica Acta, Vol. 141
Production of Methane and Ethylene in Electrochemical Reduction of Carbon Dioxide at Copper Electrode in Aqueous Hydrogencarbonate Solution
journal, June 1986
- Hori, Yoshio; Kikuchi, Katsuhei; Murata, Akira
- Chemistry Letters, Vol. 15, Issue 6
Kinetic studies of the electrolytic reduction of carbon dioxide on the mercury electrode
journal, December 1969
- Paik, W.; Andersen, T. N.; Eyring, H.
- Electrochimica Acta, Vol. 14, Issue 12
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
An electrogenerative acidobasic cell utilizing biomass for the generation of electricity and molecular hydrogen
journal, November 1993
- Kyriacou, D.; Jahngen, E. G. E.
- Journal of Applied Electrochemistry, Vol. 23, Issue 11
Effect of Cations on the Electrochemical Conversion of CO2 to CO
journal, November 2012
- Thorson, M. R.; Siil, K. I.; Kenis, P. J. A.
- Journal of the Electrochemical Society, Vol. 160, Issue 1, p. F69-F74
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
Influence of cation adsorption on the kinetics of electrode processes
journal, January 1959
- Frumkin, A. N.
- Transactions of the Faraday Society, Vol. 55
The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009
- Strmcnik, D.; Kodama, K.; van der Vliet, D.
- Nature Chemistry, Vol. 1, Issue 6
Steric effects in the dynamics of electrolytes at large applied voltages. I. Double-layer charging
journal, February 2007
- Kilic, Mustafa Sabri; Bazant, Martin Z.; Ajdari, Armand
- Physical Review E, Vol. 75, Issue 2
Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer
journal, June 2015
- Kim, Byoungsu; Ma, Sichao; Molly Jhong, Huei-Ru
- Electrochimica Acta, Vol. 166, p. 271-276
Acceleration of the reduction of carbon dioxide in the presence of multivalent cations
journal, September 2012
- Schizodimou, Agoritsa; Kyriacou, Georgios
- Electrochimica Acta, Vol. 78