Water and Solute Activities Regulate CO2 Reduction in Gas-Diffusion Electrodes

Nesbitt, Nathan T.; Smith, Wilson A.

doi:10.1021/acs.jpcc.1c01923

Title: Water and Solute Activities Regulate CO₂ Reduction in Gas-Diffusion Electrodes

Journal Article · Tue May 25 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c01923· OSTI ID:1787245

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National Renewable Energy Lab. (NREL), Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)

Electrolysis of CO₂ at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm^–2, where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO₂ to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO₂ by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO₂ to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm^–2 at the inlet had only ~0.3 A cm^–2 at the outlet for a conversion in CO₂ partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1787245

Report Number(s):: NREL/JA-5900-78623; MainId:32540; UUID:0625df18-d4eb-4cd5-a06d-8f17ad80d520; MainAdminID:24570

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 24; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 electrolysis
CO2 reduction
concentrated electrolytes
gas-diffusion electrodes
high current density
KOH
NaOH
solute activity
water activity

Title: Water and Solute Activities Regulate CO2 Reduction in Gas-Diffusion Electrodes

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References (63)

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Title: Water and Solute Activities Regulate CO₂ Reduction in Gas-Diffusion Electrodes