Mechanism of CO2 Capture and Release on Redox-Active Organic Electrodes

The mechanism of faradaic electro-swing for CO2 capture/release on a redox-active organic electrode is studied from the point of view of realizing a reversible process for CO2 separation. First, the cyclic voltammograms (CVs) of two redox-active organic monomers, anthraquinone (AQ) and 2,1,3-benzothiadiazole (BTZ), were measured under a CO2 atmosphere. The waveforms of CVs of the two redox-active organic monomers are altered under a CO2 atmosphere relative to a N2 atmosphere. There is a change in the number of redox waves from two to one for AQ and a change from reversible to irreversible waves for BTZ. To further understand the mechanisms of CO2 capture/release on redox-active organic compounds, redox-active polymer electrodes coated with polyanthraquinone (PAQ) and polybenzothiadiazole (PBTZ) were investigated using a spectroscopic analysis known as in situ attenuated total reflectance–surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS) as well as density functional theory (DFT) calculations. The CVs measured with two redox-active polymer electrodes have more positive shifts of reduction potentials for PAQ and PBTZ under a CO2 atmosphere than under an N2 atmosphere, as measured versus Ag/AgNO3: −1.8 and −1.4 V → −1.4 and −0.9 V for PAQ and −2.5 V → −2.1 and −1.9 V for PBTZ. In addition, the oxidation current on the PBTZ electrode disappears only under a CO2 atmosphere. DFT calculations indicate that the positive shifts of reduction potentials in the two electrodes under CO2 conditions are due to an exergonic adsorption reaction of CO2 onto the redox-active organic compounds. To clarify the reaction behavior between CO2 and the redox-active organic electrode, an ATR–SEIRAS spectroscopic analysis was performed. Infrared peaks are observed at 2200 and 2100 cm–1 for PAQ and PBTZ electrodes, respectively, under a CO2 atmosphere, which have been confirmed by measurements under a 13CO2 atmosphere to have adsorbed CO2. The wavenumbers corresponding to the CO2 molecules adsorbed on the two electrodes are different. These findings indicate that one electron reduction and CO2 adsorption for each redox-active organic compound are occurring simultaneously. The calculated adsorption energy of CO2 for two redox-active organic electrodes indicates that the adsorption energies of two CO2 molecules for AQ and BTZ are −7.3 and −36.3 kJ/mol. The larger adsorption energy in BTZ than that in AQ is clearly related to the disappearance of the oxidation current. However, both adsorption energies indicating adsorption of CO2 onto organic units are less than the covalent bond energies of common organic compounds, indicating that such weak adsorptions are suitable for the faradaic electro-swing of CO2 capture/release on the redox-active organic units.