A comprehensive comparative DFT study on adsorption and reactions involved in vinyl acetate synthesis from acetoxylation of ethylene on pure Pd(100) and Pd-Au(100): Elucidating the role of Au

Abstract Firstly, with DFT, electronic properties of Pd(100) and Pd-Au(100) were examined and it was found that addition of Au into Pd increases the electron density of Pd d-band. Besides, adsorption of relevant species involved in Samanos mechanism and Moiseev mechanism on Pd(100) and Pd-Au(100) was investigated and it was discovered that addition of Au impairs adsorption of species on metal surfaces. Finally, activation energies of all the reactions on Pd(100) and Pd-Au(100) were compared. Our calculations suggested that the rate-limiting step of the Samanos pathway on Pd(100) and Pd-Au(100) is the dehydrogenation of hydrogenated vinyl acetate. The rate-limiting step of the Moiseev pathway on Pd(100) is the coupling of vinyl with acetate, while that on Pd-Au(100) is the dehydrogenation of ethylene. The activation energies that are only involved in the Samanos mechanism become higher on Pd-Au(100) than on pure Pd(100), suggesting that alloying of Au is kinetically unfavorable for Samonos mechanism. Alloying of Au changes the rate-limiting step of Moiseev pathway, and Moiseev mechanism is preferred on Pd-Au(100).