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

Abstract

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 O2, 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 O2 binding and therefore various routes for methane oxidation are possible. The activation barriers for methane oxidation via various paths vary from ~83 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.