The hexagonal boron nitride (h-BN)is traditionally considered to be inert. In sharp contrast to the inert behavior of freestanding hexagonal boron nitride (h-BN), we propose the catalytic property of h-BN monolayer on Ni(111) substrate using first-principles density functional theory investigation. The interaction of O₂ molecule with the hBN/Ni(111) substrate results in nondissociative adsorption of the molecule along with elongation ofthe 0-0 bond. This can be considered as the
activated stateoEthe O 2 molecule. Further interaction of this. complex viz 0₂-h-BN/Ni(111) with an incoming CO molecule leads to the spontaneous formation of CO₂, Interestingly, the CO adsorption on the h-BN/Ni(111) substrate was found to be unfavorable, thereby implying the oxidation of CO selectively through Eley-Rideal (ER) mechanism.