Mechanistic Insights into the Reduction of CO₂ on Tin Electrodes using in Situ ATR-IR Spectroscopy

The reduction of CO2 on tin cathodes was studied using in situ attenuated total reflectance infrared spectroscopy (ATR-IR). Thin films of a mixed Sn/SnOx species were deposited onto a single-crystal ZnSe ATR crystal. Peaks centered at about 1500, 1385, and 1100 cm–1, attributed to a surface-bound monodentate tin carbonate species, were consistently present under conditions at which CO2 reduction takes place. It was shown that these peaks are only present at potentials where CO2 reduction is observed. Moreover, these peaks disappear if the pH of the reaction is too low or if the tin surface is chemically etched to remove surface oxide. Sn6O4(OH)4 and SnO2 nanoparticles were shown to be catalytically active for CO2 reduction, and insights into the oxidation state of the catalytically active species are gained from a comparison of the catalytic behavior of the two nanoparticle species. From these experiments, a mechanism governing the reduction of CO2 on tin electrodes is proposed.