Mechanistic Study of the Electrochemical Reduction of CO2 in Aprotic Ionic Liquid in Air.

The capture and electrochemical conversion of dilute CO2 in air is a promising approach to mitigate global warming. Aiming to increase the efficiency of the electrochemical reduction of CO2, 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 316L, was compared in an aprotic ionic liquid as the electrolyte to monitor the CO2 concentration and chemical reactions using a CO2 sensor and diffuse reflectance infrared Fourier transform spectroscopy and Raman spectroscopy in CO2/N2 (400 ppm CO2 and 99.96% N2) or synthetic air (400 ppm CO2, 21% O2, and 79% N2). The CO2 concentration decreased at negative potentials and was more drastic in synthetic air than in CO2/N2. 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 (O2•-), produced by the reduction of O2 on each electrode, promotes the electrochemical reduction of CO2 whose reduction potential is higher on the negative side than that of O2. This research deepens our understanding of the electrochemical capture/release and conversion of dilute CO2.

NOx Storage Performance at Low Temperature over Platinum Group Metal-Free SrTiO3-Based Material.

Pt-based catalysts are commonly employed as NOx-trapping catalysts for automobiles, while perovskite oxides have received attention as Pt-free NOx-trapping catalysts. However, the NOx storage performance of perovskite catalysts is significantly inferior at low temperatures and with coexisting gases such as H2O, CO2, and SO2. This study demonstrates that NOx storage reactions proceed over redox site (Mn, Fe, and Co)-doped SrTiO3 perovskites. Among the examined catalysts, Mn-doped SrTiO3 exhibited the highest NOx storage capacity (NSC) and showed a high NSC even at a low temperature of 323 K. Moreover, the high NOx storage performance of Mn-doped SrTiO3 was retained in the presence of poisoning gases (H2O, CO2, and SO2). NO oxidation experiments revealed that the NSC of Co-doped SrTiO3 was dependent on the NO oxidation activity from NO to NO2 via lattice oxygen, which resulted in an inferior NSC at low temperatures. On the other hand, Mn-doped SrTiO3 successfully adsorbed NO molecules onto its surface at 323 K without the NO oxidation process using lattice oxygens. This unique adsorption behavior of Mn-doped SrTiO3 was concluded to be responsible for the high NSC in the presence of poisoning gases.