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  4. Operando Observation of (Bi)carbonate Precipitation during Electrochemical CO2 Reduction in Strongly Acidic Electrolytes
 
research article

Operando Observation of (Bi)carbonate Precipitation during Electrochemical CO2 Reduction in Strongly Acidic Electrolytes

Bernasconi, Francesco
•
Plainpan, Nukorn
•
Mirolo, Marta
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May 13, 2024
Acs Catalysis

Precipitation of (bi)carbonate salts during the electrochemical CO2 reduction (CO2RR) has been identified as a major cause of degradation and one of the main challenges to be overcome before implementing this technology on the industrial scale. Recently, the use of acidic electrolytes has been suggested as a promising strategy to avoid this undesirable precipitation of carbonates and maximize the conversion of CO2 into valuable products. However, direct experimental evidence supporting this claim, as well as an understanding of degradation mechanisms in acidic electrolytes, is currently missing. In this study, we use operando synchrotron wide-angle X-ray scattering to provide unambiguous experimental proof that substantial (bi)carbonate precipitation takes place in Ag and Cu gas diffusion electrodes (GDEs) during CO2RR even in strongly acidic electrolytes (pH 1). The (bi)carbonate signal intensity increases over time, correlating with a loss of selectivity for carbon products and an increased level of H-2 production. Electrochemical measurements coupled with products analysis also show that a minimum current is required to activate the CO2RR and suppress hydrogen evolution and that this current is higher for more acidic electrolytes. These findings provide experimental evidence for high local pH close to the catalyst even in acidic electrolytes. Our results confirm that the CO2RR performed in an acidic electrolyte can yield high selectivity to carbon products, provided sufficiently large current densities are applied to provoke local proton depletion in the vicinity of the catalyst, but that detrimental (bi)carbonate precipitation and selectivity losses occur even under these conditions.

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Type
research article
DOI
10.1021/acscatal.4c01884
Web of Science ID

WOS:001225228600001

Author(s)
Bernasconi, Francesco
•
Plainpan, Nukorn
•
Mirolo, Marta
•
Wang, Qing
•
Zeng, Peng
•
Battaglia, Corsin  
•
Senocrate, Alessandro
Date Issued

2024-05-13

Publisher

Amer Chemical Soc

Published in
Acs Catalysis
Volume

14

Issue

11

Start page

8232

End page

8237

Subjects

Physical Sciences

•

Co2 Reduction

•

Electrocatalysis

•

Gas Diffusion Electrodes

•

Acidic Electrolyte

•

Carbonatesprecipitation

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
PV-LAB  
FunderGrant Number

NCCR Catalysis, National Centre of Competence in Research

Swiss National Science Foundation

180544

ETH Board in the framework of the Joint Strategic Initiative

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Available on Infoscience
June 5, 2024
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/208393
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