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Electrochemical CO2separation has drawn attention as a promising strategy for using renewable energy to mitigate climate change. Redox-active compounds that undergo proton-coupled electron transfer (PCET) are an impetus for pH-swing-driven CO2capture at low energetic costs. However, multiple barriers hinder this technology from maturing, including sensitivity to oxygen and the slow kinetics of CO2capture. Here, we use vapor phase chemistry to construct a textile electrode comprising an immobilized PCET agent, poly(1-aminoanthraquinone) (PAAQ), and incorporate it into redox flow cells. This design contrasts with others that use dissolved PCET agents by confining proton-storage to the surface of an electrode kept separate from an aqueous, CO2-capturing phase. This system facilitates carbon capture from gaseous sources (a 1% CO2feed and air), as well as seawater, with the latter at an energetic cost of 202 kJ/molCO2, and we find that quinone moieties embedded within the electrode are more stable to oxygen than dissolved counterparts. Simulations using a 1D reaction-transport model show that moderate energetic costs should be possible for air capture of CO2with higher loadings of polymer-bound PCET moieties. The remarkable stability of this system sets the stage for producing textile-based electrodes that facilitate pH-swing-driven carbon capture in practical situations.
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pH swing cycle for CO 2 capture electrochemically driven through proton-coupled electron transfer
We perform a thermodynamic analysis of the energetic cost of CO 2 separation from flue gas (0.1 bar CO 2 (g)) and air (400 ppm CO 2 ) using a pH swing created by electrochemical redox reactions involving proton-coupled electron transfer from molecular species in aqueous electrolyte. In this scheme, electrochemical reduction of these molecules results in the formation of alkaline solution, into which CO 2 is absorbed; subsequent electrochemical oxidation of the reduced molecules results in the acidification of the solution, triggering the release of pure CO 2 gas. We examined the effect of buffering from the CO 2 –carbonate system on the solution pH during the cycle, and thereby on the open-circuit potential of an electrochemical cell in an idealized four-process CO 2 capture-release cycle. The minimum work input varies from 16 to 75 kJ mol CO2 −1 as throughput increases, for both flue gas and direct air capture, with the potential to go substantially lower if CO 2 capture or release is performed simultaneously with electrochemical reduction or oxidation. We discuss the properties required of molecules that would be suitable for such a cycle. We also demonstrate multiple experimental cycles of an electrochemical CO 2 capture and release system using 0.078 M sodium 3,3′-(phenazine-2,3-diylbis(oxy))bis(propane-1-sulfonate) as the proton carrier in an aqueous flow cell. CO 2 capture and release are both performed at 0.465 bar at a variety of current densities. When extrapolated to infinitesimal current density we obtain an experimental cycle work of 47.0 kJ mol CO2 −1 . This result suggests that, in the presence of a 0.465 bar/1.0 bar inlet/outlet pressure ratio, a 1.9 kJ mol CO2 −1 thermodynamic penalty should add to the measured value, yielding an energy cost of 48.9 kJ mol CO2 −1 in the low-current-density limit. This result is within a factor of two of the ideal cycle work of 34 kJ mol CO2 −1 for capturing at 0.465 bar and releasing at 1.0 bar. The ideal cycle work and experimental cycle work values are compared with those for other electrochemical and thermal CO 2 separation methods.
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- Award ID(s):
- 1914543
- PAR ID:
- 10312649
- Date Published:
- Journal Name:
- Energy & Environmental Science
- Volume:
- 13
- Issue:
- 10
- ISSN:
- 1754-5692
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0EE01834A
