Modeling C–H Bond Activation and Oxidations of Alkanes over Cu–MOR Using First-Principles Methods

Direct conversion of methane to methanol can significantly boost the economic value of shale gas utilization. However, the stable C–H bond makes methane partial oxidation a challenging catalysis task. At low temperatures, C–H bond activation is kinetically sluggish. On the other hand, methane is likely oxidized fully into CO2 at high temperatures, which will lower methanol selectivity. Several Cu–oxo complexes such as mono­(μ-oxo)­dicopper, bis­(μ-oxo)­dicopper, and copper trioxo anchored in the mordenite (MOR) zeolite framework are shown to balance catalytic activity and product selectivity for the methane-to-methanol conversion. In this work, the thermodynamic stability of Cu–oxo complexes was evaluated as active centers for C–H bond activation using the BEEF-vdW functional within the density functional theory (DFT) framework, and the bis­(μ-oxo)­dicopper moiety was identified as the most stable configuration. The catalytic reactivity of these complexes was then tested with the activation of the first C–H bond of light hydrocarbons (i.e., methane, ethane, and propane), as well as subsequent oxidation steps to corresponding alcohols. Site II of the Cu–trioxo cluster with highest spin density remains as the most potent active site by enabling the lowest energy barrier for initial methane activation when electronic spin crossing was considered. Energy barriers for the first C–H activation step follow a decreasing order of methane, ethane, and propane