Mapping the Catalytic-Space for the Reactivity of Metal-free Boron Nitride with O2 for H2O-Mediated Conversion of Methane to HCHO and CO

Transition-metal based catalysts have been widely employed to catalyze partial oxidation of light alkanes. Recently, metal-free hexagonal-boron nitride (h-BN) has emerged as a promising catalyst for the oxidation of CH4 to HCHO and CO; however, the intricate catalytic surface of h-BN at molecular and electronic levels remains inadequately understood. Key questions include how electron-deficient boron atoms in h-BN reduce O-2, and whether the partial oxidation of methane over h-BN exhibits similarities to traditional transition-metal catalysts. In our study, we computationally-mapped in-detail the surface catalytic-space of h-BN for methane oxidation. We considered different structures of h-BN and show that these structures contain numerous sites for O-2 binding and therefore various routes for methane oxidation are possible. The activation barriers for methane oxidation via various paths varies from similar to 83 to similar to 123 kcal mol(-1). To comprehend the differences in activation barriers, we employed geometrical, orbital and distortion/interaction analysis (DIA). Orbital analysis reveals that methane activation over h-BN in presence of dioxygen follows a standard hydrogen atom transfer mechanism. It is also shown that water plays an intriguing role in reducing the barrier for HCHO and CO formation by acting as a bridge.