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research article

Surface Charge Boundary Condition Often Misused in CO2 Reduction Models

Johnson, Evan F.
•
Boutin, Etienne  
•
Haussener, Sophia  
September 8, 2023
Journal Of Physical Chemistry C

The Poisson-Nernst-Planck equations have been used to model species transport in electrochemical CO2 reduction, where the surface charge boundary condition accounts for the potential drop across the Stern layer. A direct comparison of the published models reveals the relative permittivity inside the Stern layer has been applied inconsistently across the literature, with values ranging from 6 to 80.1. In fact, a majority of studies use the pure water or electrolyte permittivity value inside the Stern layer, implying a Stern layer capacitance in the range of 100-200 mu F cm(-2). This is far higher than the Stern layer capacitances measured in fundamental experiments of the electric double layer, typically in the range of 20-25 mu F cm(-2). Using such a high capacitance supercharges the electric field in the diffuse layer, leading to an overestimate of the electrolyte cation concentration, extreme pH and pOH values, and-if steric effects are included-a vast underestimation of the CO2 concentration at the reaction plane. The discrepancy can be traced back to the surface charge boundary condition, which is explained in detail herein. Previously published CO2R models that used such a high Stern layer capacitance or permittivity are expected to have overpredicted the effects of the electric double layer.

  • Details
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Type
research article
DOI
10.1021/acs.jpcc.3c05364
Web of Science ID

WOS:001065400100001

Author(s)
Johnson, Evan F.
Boutin, Etienne  
Haussener, Sophia  
Date Issued

2023-09-08

Publisher

AMER CHEMICAL SOC

Published in
Journal Of Physical Chemistry C
Volume

127

Issue

37

Start page

18784

End page

18790

Subjects

Chemistry, Physical

•

Nanoscience & Nanotechnology

•

Materials Science, Multidisciplinary

•

Chemistry

•

Science & Technology - Other Topics

•

Materials Science

•

double-layer

•

silver

•

electrolytes

•

adsorption

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LRESE  
Available on Infoscience
October 23, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/201702
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