CO oxidation on h-BN supported Au atom
The mechanism of CO oxidation by O{sub 2} on Au atoms supported on the pristine and defected hexagonal boron nitride (h-BN) surface has been studied theoretically using density functional theory. It is found that O{sub 2} binds stronger than CO on an Au atom supported on the defect free h-BN surface and h-BN surface with nitrogen vacancy (V{sub N}-h-BN), but weaker than CO on a free Au atom or Au trapped by a boron vacancy (V{sub B}-h-BN). The excess of the positive or negative charge on Au can considerably change its catalytic properties and enhance activation of the adsorbed O{sub 2}. Coadsorption of CO and O{sub 2} on Au, Au/V{sub N}-h-BN, and Au/V{sub B}-h-BN results in additional charge transfer to O{sub 2}. Various pathways of the CO oxidation reaction by molecular oxygen are studied. We found two different pathways for CO oxidation: a two-step pathway where two CO{sub 2} molecules are formed independently, and a self-promotion pathway where oxidation of the first CO molecule is promoted by the second CO molecule. Interaction of Au with the defect-free and defected h-BN surface considerably affects the CO oxidation reaction pathways and barriers. Therefore, Au supported on the h-BN surface (pristine or defected) cannot be considered as pseudo-free atom and support effects have to be taken into account, even when the interaction of Au with the support is weak.