Thin-film TiO2 electrode surface characterization upon CO2 reduction processes

The effect of electrochemical reduction of CO2 on the structure and morphology of titanium(IV) oxide thin films was examined after a fixed-potential bulk electrolysis process. Films deposited on ITO (Indium-Tin Oxide) substrates were used as the working electrodes and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) as solvent and as supporting electrolyte. Grazing incidence X-ray diffraction analysis performed before and after the electrolysis process indicated no microstructural changes of the anatase films. X-ray photoelectron spectroscopy revealed peaks associated with adsorbed carbonate ions at 288 eV and CO2 species at 293 eV, whereas Ti2p peaks displacements for CO2-saturated TiO2/ITO surfaces in [BMIm][BF4] revealed chemical bonding effects. Auger electron spectroscopy revealed a high carbon content on CO2-exposed films, and suggested a strong chemisorption of CO2 and CO32- stop species on the TiO2/ITO surface in [BMIm][BF4] solvent system. A significant decrease in carbon content after bulk electrolysis indicated that the CO2 electroreduction process is not controlled by either diffusion or by adsorption of CO2 on the TiO2/ITO electrode surface.