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Title: Using a 3D Porous Flow-Through Electrode Geometry for High-Rate Electrochemical Reduction of CO2 to CO in Ionic Liquid

Abstract

Three-dimensional porous flow-through electrodes promise the realization of higher current densities in the electrochemical carbon dioxide reduction reaction (CO2RR) by overcoming mass-transport limitations associated with the diffusion of dissolved CO2 in the bulk electrolyte. Using an ionic-liquid-based electrolyte, [EMIM]BF4, offers the additional benefit of higher CO2 solubility compared to water-based electrolytes. Here, we quantitatively evaluated the effects of flow-driven reactant transport on electrode activity and selectivity for the electrochemical CO2RR in [EMIM]BF4. High-surface-area porous flow-through electrodes were fabricated by wet-chemical deposition of Ag nanoflowers on commercial macroporous Al foams. At the highest electrolyte flow-through rate of 100 mL min–1, we observed a 70-fold increase in partial CO current density, and a 7-fold increase in the Faradaic efficiency toward CO, from 10% without flow to 75% with flow. At the same time, the selectivity changed from oxalate as the main product without flow to CO in the electrolyte flow-through configuration. These results demonstrate that the flow-through approach provides a promising path forward to control selectivity and to overcome mass-transport limitations of the electrochemical CO2RR.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1630811
Report Number(s):
LLNL-JRNL-782157
Journal ID: ISSN 2155-5435; 976694
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; flow-through electrochemistry; ionic liquid; CO2 reduction; porous electrode

Citation Formats

Vedharathinam, Vedasri, Qi, Zhen, Horwood, Corie, Bourcier, Bill, Stadermann, Michael, Biener, Juergen, and Biener, Monika. Using a 3D Porous Flow-Through Electrode Geometry for High-Rate Electrochemical Reduction of CO2 to CO in Ionic Liquid. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b03201.
Vedharathinam, Vedasri, Qi, Zhen, Horwood, Corie, Bourcier, Bill, Stadermann, Michael, Biener, Juergen, & Biener, Monika. Using a 3D Porous Flow-Through Electrode Geometry for High-Rate Electrochemical Reduction of CO2 to CO in Ionic Liquid. United States. https://doi.org/10.1021/acscatal.9b03201
Vedharathinam, Vedasri, Qi, Zhen, Horwood, Corie, Bourcier, Bill, Stadermann, Michael, Biener, Juergen, and Biener, Monika. 2019. "Using a 3D Porous Flow-Through Electrode Geometry for High-Rate Electrochemical Reduction of CO2 to CO in Ionic Liquid". United States. https://doi.org/10.1021/acscatal.9b03201. https://www.osti.gov/servlets/purl/1630811.
@article{osti_1630811,
title = {Using a 3D Porous Flow-Through Electrode Geometry for High-Rate Electrochemical Reduction of CO2 to CO in Ionic Liquid},
author = {Vedharathinam, Vedasri and Qi, Zhen and Horwood, Corie and Bourcier, Bill and Stadermann, Michael and Biener, Juergen and Biener, Monika},
abstractNote = {Three-dimensional porous flow-through electrodes promise the realization of higher current densities in the electrochemical carbon dioxide reduction reaction (CO2RR) by overcoming mass-transport limitations associated with the diffusion of dissolved CO2 in the bulk electrolyte. Using an ionic-liquid-based electrolyte, [EMIM]BF4, offers the additional benefit of higher CO2 solubility compared to water-based electrolytes. Here, we quantitatively evaluated the effects of flow-driven reactant transport on electrode activity and selectivity for the electrochemical CO2RR in [EMIM]BF4. High-surface-area porous flow-through electrodes were fabricated by wet-chemical deposition of Ag nanoflowers on commercial macroporous Al foams. At the highest electrolyte flow-through rate of 100 mL min–1, we observed a 70-fold increase in partial CO current density, and a 7-fold increase in the Faradaic efficiency toward CO, from 10% without flow to 75% with flow. At the same time, the selectivity changed from oxalate as the main product without flow to CO in the electrolyte flow-through configuration. These results demonstrate that the flow-through approach provides a promising path forward to control selectivity and to overcome mass-transport limitations of the electrochemical CO2RR.},
doi = {10.1021/acscatal.9b03201},
url = {https://www.osti.gov/biblio/1630811}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 12,
volume = 9,
place = {United States},
year = {Fri Oct 11 00:00:00 EDT 2019},
month = {Fri Oct 11 00:00:00 EDT 2019}
}

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Cited by: 24 works
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Figures / Tables:

Figure 1 Figure 1: (a) Schematic illustration of the flow-through porous cathode configuration, (b) Low (5000 x) magnification SEM image of the Ag coated Al foam flow-through electrode. Inset showing the nanoflower morphology of the Ag coating at 50000 x, (c) CVs of the 3D Ag coated Al foam working electrode inmore » 0.1M HClO4 at scan rates ranging from 10 to 200 mV s -1, and (d) Al foam working electrode charging current vs. scan rate (υ) with and without the Ag nanoflower coating.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.