Modeling the Local Environment within Porous Electrode during Electrochemical Reduction of Bicarbonate
Abstract
The electrochemical reduction of bicarbonate to renewable chemicals without external gaseous CO2 supply has been motivated as a means of integrating conversion with upstream CO2 capture. The way that CO2 is formed and transported during CO2-mediated bicarbonate reduction in flow cells is profoundly different from conventional CO2 saturated and gas-fed systems and a thorough understanding of the process would allow further advancements. Here, we report a comprehensive two-phase mass transport model to estimate the local concentration of species in the porous electrode resultant from homogeneous and electrochemical reactions of (bi)carbonate and CO2. The model indicates that significant CO2 is generated in the porous electrode during electrochemical reduction, even though the starting bicarbonate solution contains negligible CO2. However, the in situ formation of CO2 and subsequent reduction to CO exhibits a plateau at high potentials due to neutralization of the protons by the alkaline reaction products, acting as the limiting step toward higher CO current densities. Nevertheless, the pH in the catalyst layer exhibits a relatively smaller rise, compared to conventional electrochemical CO2 reduction cells, because of the reaction between protons and CO3 2– and OH– that is confined to a relatively small volume. A large fraction of the CL exhibitsmore »
- Authors:
-
- National Renewable Energy Laboratory, Golden, Colorado 80401, United States, Renewable and Sustainable Energy Institute (RASEI), University of Colorado Boulder, Boulder, Colorado 80303, United States
- Materials for Energy Conversion and Storage (MECS), Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, van der Maasweg 9, 2629 HZ Delft, The Netherlands
- Renewable and Sustainable Energy Institute (RASEI), University of Colorado Boulder, Boulder, Colorado 80303, United States, Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, Colorado 80303, United States
- National Renewable Energy Laboratory, Golden, Colorado 80401, United States, Renewable and Sustainable Energy Institute (RASEI), University of Colorado Boulder, Boulder, Colorado 80303, United States, Materials for Energy Conversion and Storage (MECS), Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, van der Maasweg 9, 2629 HZ Delft, The Netherlands, Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, Colorado 80303, United States
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1864387
- Alternate Identifier(s):
- OSTI ID: 1867378; OSTI ID: 1878469
- Report Number(s):
- NREL/JA-5900-81991
Journal ID: ISSN 0888-5885
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- Industrial and Engineering Chemistry Research
- Additional Journal Information:
- Journal Name: Industrial and Engineering Chemistry Research Journal Volume: 61 Journal Issue: 29; Journal ID: ISSN 0888-5885
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrical properties; Electrochemical cells; Electrodes; Electrolytes,; Membranes; Multiscale modeling; Electrocatalysis; CO2
Citation Formats
Kas, Recep, Yang, Kailun, Yewale, Gaurav P., Crow, Allison, Burdyny, Thomas, and Smith, Wilson A. Modeling the Local Environment within Porous Electrode during Electrochemical Reduction of Bicarbonate. United States: N. p., 2022.
Web. doi:10.1021/acs.iecr.2c00352.
Kas, Recep, Yang, Kailun, Yewale, Gaurav P., Crow, Allison, Burdyny, Thomas, & Smith, Wilson A. Modeling the Local Environment within Porous Electrode during Electrochemical Reduction of Bicarbonate. United States. https://doi.org/10.1021/acs.iecr.2c00352
Kas, Recep, Yang, Kailun, Yewale, Gaurav P., Crow, Allison, Burdyny, Thomas, and Smith, Wilson A. Fri .
"Modeling the Local Environment within Porous Electrode during Electrochemical Reduction of Bicarbonate". United States. https://doi.org/10.1021/acs.iecr.2c00352.
@article{osti_1864387,
title = {Modeling the Local Environment within Porous Electrode during Electrochemical Reduction of Bicarbonate},
author = {Kas, Recep and Yang, Kailun and Yewale, Gaurav P. and Crow, Allison and Burdyny, Thomas and Smith, Wilson A.},
abstractNote = {The electrochemical reduction of bicarbonate to renewable chemicals without external gaseous CO2 supply has been motivated as a means of integrating conversion with upstream CO2 capture. The way that CO2 is formed and transported during CO2-mediated bicarbonate reduction in flow cells is profoundly different from conventional CO2 saturated and gas-fed systems and a thorough understanding of the process would allow further advancements. Here, we report a comprehensive two-phase mass transport model to estimate the local concentration of species in the porous electrode resultant from homogeneous and electrochemical reactions of (bi)carbonate and CO2. The model indicates that significant CO2 is generated in the porous electrode during electrochemical reduction, even though the starting bicarbonate solution contains negligible CO2. However, the in situ formation of CO2 and subsequent reduction to CO exhibits a plateau at high potentials due to neutralization of the protons by the alkaline reaction products, acting as the limiting step toward higher CO current densities. Nevertheless, the pH in the catalyst layer exhibits a relatively smaller rise, compared to conventional electrochemical CO2 reduction cells, because of the reaction between protons and CO3 2– and OH– that is confined to a relatively small volume. A large fraction of the CL exhibits a mildly alkaline environment at high current densities, while an appreciable amount of carbonic acid (0.1–1 mM) and a lower pH exist adjacent to the membrane, which locally favor hydrogen evolution, especially at low electrolyte concentrations. The results presented here provide insights into local cathodic conditions for both bicarbonate cells and direct-CO2 reduction membrane electrode assembly cells utilizing cation exchange membranes facing the cathode.},
doi = {10.1021/acs.iecr.2c00352},
journal = {Industrial and Engineering Chemistry Research},
number = 29,
volume = 61,
place = {United States},
year = {Fri Apr 22 00:00:00 EDT 2022},
month = {Fri Apr 22 00:00:00 EDT 2022}
}
https://doi.org/10.1021/acs.iecr.2c00352
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