Au core stabilizes CO adsorption onto Pd leading to CO2 production

Abstract

Au core and Pd shell supported on carbon structure Au@Pd/C can cleave the C–C bond of ethanol molecules leading to the production of a relatively high amount of CO2 when compared with Pd/C electrocatalyst as the attenuated total reflectance - Fourier transform infrared (ATR-FTIR) experiment shows. Density functional theory (DFT) calculations showed that this could be explained by the oxidation of CO species adsorbed into Pd sites that has a modified electronic structure compared with Pd/C. In terms of DFT analysis, the highest thermodynamical stability of CO in Pd shell with Au core atoms, when compared with Pd/C is because of the increase of virtual orbital states near Fermi level that can be occupied by valence electrons of CO molecule. The d-band center shift is experimentally verified using the valence band X-ray photoelectron spectroscopy and theoretically predicted by the Generalized Koopmans’ Theorem. Besides that, Au@Pd/C electrocatalyst has a better electrochemical activity when compared with Pd/C.

Keywords

• Au@Pd/C
• Koopmans' theorem
• Density functional theory
• Density of states
• Ethanol oxidation reaction