Comparative theoretical study of CO activation on clean and potassium-preadsorbed low index surfaces of transition metals.

Context: The efficient catalysis of CO adsorption and activation presents a formidable challenge due to its pronounced thermodynamic stability and kinetic inertia. Previous experiments have left gaps in understanding the promotional effects and underlying mechanism of potassium. In this study, we systematically investigate CO adsorption and activation on clean and potassium-preadsorbed low index surfaces of transition metals. Theoretical results reveal a substantial augmentation in CO binding strength when potassium is introduced, concomitant with a general reduction in activation energies. Notably, linear correlations are significant on close-packed metal surfaces without and with potassium additive. Through a comprehensive analysis encompassing geometric parameters, electronic structures, and energy decomposition, we discern the physical underpinnings of the potassium effect. This enhancement is primarily ascribed to direct electron transfer and dipole-dipole interactions. Furthermore, we scrutinize the impact of an external electric field, demonstrating that the application of a negative electric field accelerates CO activation, mirroring the effects observed with potassium.

Methods: All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave method (PAW). Throughout the entire work, the Bayesian error estimation functional (BEEF) was used.