Mechanistic Insights into Radical-Induced Selective Oxidation of Methane over Nonmetallic Boron Nitride Catalysts.

Boron-based nonmetallic materials (such as B 2 O 3 and BN) emerge as promising catalysts for selective oxidation of light alkanes by O 2 to form value-added products, resulting from their unique advantage in suppressing CO 2 formation. However, the site requirements and reaction mechanism of these boron-based catalysts are still in vigorous debate, especially for methane (the most stable and abundant alkane). Here, we show that hexagonal BN ( h -BN) exhibits high selectivities to formaldehyde and CO in catalyzing aerobic oxidation of methane, similar to Al 2 O 3 -supported B 2 O 3 catalysts, while h -BN requires an extra induction period to reach a steady state. According to various structural characterizations, we find that active boron oxide species are gradually formed in situ on the surface of h -BN, which accounts for the observed induction period. Unexpectedly, kinetic studies on the effects of void space, catalyst loading, and methane conversion all indicate that h -BN merely acts as a radical generator to induce gas-phase radical reactions of methane oxidation, in contrast to the predominant surface reactions on B 2 O 3 /Al 2 O 3 catalysts. Consequently, a revised kinetic model is developed to accurately describe the gas-phase radical feature of methane oxidation over h -BN. With the aid of in situ synchrotron vacuum ultraviolet photoionization mass spectroscopy, the methyl radical (CH 3 • ) is further verified as the primary reactive species that triggers the gas-phase methane oxidation network. Theoretical calculations elucidate that the moderate H-abstraction ability of predominant CH 3 • and CH 3 OO • radicals renders an easier control of the methane oxidation selectivity compared to other oxygen-containing radicals generally proposed for such processes, bringing deeper understanding of the excellent anti-overoxidation ability of boron-based catalysts.