Electrochemical conversion of carbon dioxide into eligible fuels has become the subject of particular fundamental interest. Recently, we have reported electrochemical studies on CO₂ electroreduction at multilayered catalyst composed of the monatomic layer of copper covering palladium overlayers (0.8-10 monolayers) deposited on the well-defined Au(111) surface [1]. In this study Carbon dioxide electroreduction has been studied at ultrathin palladium layers deposited on copper electrode. The Pd deposits have been prepared by using chemical methods. The spontaneous galvanic displacement and resulting uncontrolled deposition of the palladium on copper has been entirely eliminated by the use of palladium(II). This method allowed us for controlled and precise deposition of palladium layers by electrochemical methods. The deposits coverage was changed within the range 0.5 to 5 atomic monolayers. The effectiveness of the method and the durability of the obtained ultrathin palladium layers have been confirmed by X-ray photoelectron spectroscopy (XPS). XPS has been also used for detailed analysis of the electronic properties of the Pd/Cu systems. Significant chemical interactions of both elements resulted in a partial shift of the electron density from palladium to copper and in the changes in the symmetry of 3d palladium signals characteristic for two-dimensional palladium structures (Pd monolayers). A detailed analysis of the valence band structure of Pd/Cu was correlated to the catalytic activity of the studied systems. The unique properties of the valence band structure cannot be attributed to the simple superposition of pure metal bands (Pd and Cu). It has been shown that the increase in the electron density near the Fermi level results in a significant decrease in the overpotential of the carbon dioxide electroreduction. Analysis of the gaseous products obtained in the CO₂ electroreduction was performed by gas chromatography. Adsorption of carbon dioxide on Pd/Cu layers was demonstrated by XPS measurements in the presence of 1 mbar CO₂ in XPS measurements under near ambient pressure XPS (NAP-XPS).

[1] A. Januszewska, R. Jurczakowski, P. Kulesza, Langmuir 30(2014)14314-14321