Dynamically Formed Active Sites on Liquid Boron Oxide for Selective Oxidative Dehydrogenation of Propane

Boron oxide-based catalysts have been shown to be both active and selective for driving the oxidative dehydrogenation of propane (ODHP) without the use of metal promoters. However, this reaction occurs at temperatures where boron oxide melts, challenging experimental identification of the molecular structures within the boron oxide phase under reaction conditions and thus hindering the understanding of its active sites and reaction mechanism(s). By combining density functional theory computations, ab initio molecular dynamics simulations, in situ Raman characterization, and microkinetic modeling, we propose that dimerized di-coordinated boron sites (>B-B<)- dynamically formed in liquid boron oxide-are the active species for O-2 activation under reaction conditions. The resulting peroxylike species (>B-O-O-B<) is then responsible for propane activation but is a moderate oxidant for ODHP and thus inert to propene. These peroxy-like structures rapidly activate propane, homolytically cleaving the >B-O-O-B< bond, producing a propyl radical and a >B-O-center dot dangling bond. These > B-O-center dot originate from the >B-O-O-B< sites as well as the liquid B2O3 structure itself and play a critical role in the abstraction of H atoms from propane and propyl. In fact, microkinetic modeling reveals that the formation of adsorbed C3H7* radicals is the main rate-controlling step due to the highly endergonic adsorption of propane into the system. Otherwise, the only activated processes were found to be the dehydration steps that lead to water formation, which exhibit an intriguing dependence on the concentration of surface hydroxyl species. These findings provide significant insights into the ODHP mechanisms on boron-based catalysts and emphasize the importance of understanding the liquid nature of the oxide to account for its catalytic activity.