Traditionally, h-BN is used as coating material to prevent corrosion on the metal surface. In sharp contrast to this, here we show catalytic behavior of h-BN monolayer deposited on Ni(111) surface, clearly demonstrating the influence of the support in modulation of h-BN electronic structure. Using first principles density functional theory we have studied the interaction of O-2 molecules with the h-BN/Ni(111) surface. The activation of O-O bond, which is the most important step for oxidative catalysis, showed dependence on the O-2 coverage. Thus this study is extremely important to predict the optimum O-2 pressure in reaction chamber for efficient catalysis. (C) 2017 Elsevier B.V. All rights reserved.