Mechanistic Study of the Electrochemical Reduction of CO in Aprotic Ionic Liquid in Air.

The capture and electrochemical conversion of dilute CO in air is a promising approach to mitigate global warming. Aiming to increase the efficiency of the electrochemical reduction of CO, we fabricated electrodes and developed a custom-designed sealed electrochemical reaction system to study the mechanism of this conversion. The performance of three metal electrodes, Ag, Cu, and SUS 316 L, was compared in an aprotic ionic liquid as the electrolyte to monitor the CO concentration and chemical reactions using a CO sensor and diffuse reflectance infrared Fourier transform spectroscopy and Raman spectroscopy in CO/N (400 ppm CO and 99.96 % N) or synthetic air (400 ppm CO, 21 % O, and 79 % N). The CO concentration decreased at negative potentials and was more drastic in synthetic air than in CO/N. At negative potential in synthetic air, IR revealed carbon monoxide, carbonate, or peroxydicarbonate on the Ag, Cu, or SUS 316L electrodes, respectively. Reaction intermediates were identified using Raman spectroscopy. Superoxide (O⋅), produced by the reduction of O on each electrode, promotes the electrochemical reduction of CO whose reduction potential is higher on the negative side than that of O. This research deepens our understanding of the electrochemical capture/release and conversion of dilute CO.