Trade-Off between Redox Potential and the Strength of Electrochemical CO(2) Capture in Quinones

[Image: see text] Electrochemical carbon dioxide capture recently emerged as a promising alternative approach to conventional energy-intensive carbon-capture methods. A common electrochemical capture approach is to employ redox-active molecules such as quinones. Upon electrochemical reduction, quinones become activated for the capture of CO(2) through a chemical reaction. A key disadvantage of this method is the possibility of side-reactions with oxygen, which is present in almost all gas mixtures of interest for carbon capture. This issue can potentially be mitigated by fine-tuning redox potentials through the introduction of electron-withdrawing groups on the quinone ring. In this article, we investigate the thermodynamics of the electron transfer and chemical steps of CO(2) capture in different quinone derivatives with a range of substituents. By combining density functional theory calculations and cyclic voltammetry experiments, we support a previously described trade-off between the redox potential and the strength of CO(2) capture. We show that redox potentials can readily be tuned to more positive values to impart stability to oxygen, but significant decreases in CO(2) binding free energies are observed as a consequence. Our calculations support this effect for a large series of anthraquinones and benzoquinones. Different trade-off relationships were observed for the two classes of molecules. These trade-offs must be taken into consideration in the design of improved redox-active molecules for electrochemical CO(2) capture.