Complete Reaction Cycle for Methane-to-Methanol Conversion over Cu-SSZ-13: First-Principles Calculations and Microkinetic Modeling

The steadily increasing consumption of natural gas imposes a need to facilitate the handling and distribution of the fuel, which presently is compressed or condensed. Alternatively, reduced volatility and increased tractability are achieved by converting the chemical energy of the main component, methane, into liquid methanol. Previous studies have explored direct methane-to-methanol conversion, but suitable catalysts have not yet been identified. Here, the complete reaction cycle for methane-to-methanol conversion over the Cu-SSZ-13 system is studied using density functional theory. The first step in the reaction cycle is the migration of Cu species along the zeolite framework forming the Cu pair, which is necessary for the adsorption of O2. Methane conversion occurs over the CuOOCu and CuOCu sites, consecutively, after which the system is returned to its initial structure with two separate Cu ions. A density functional theory-based kinetic model shows high activity when water is included in the reaction mechanism, for example, even at very low partial pressures of water, the kinetic model results in a turnover frequency of ∼1 at 450 K. The apparent activation energy from the kinetic model (∼1.1 eV) is close to recent measurements. However, experimental studies always observe very small amounts of methanol compared to formation of more energetically preferred products, for example, CO2. This low selectivity to methanol is not described by the current reaction mechanism as it does not consider formation of other species; however, the results suggest that selectivity, rather than inherent kinetic limitations, is an important target for improving methanol yields from humid systems. Moreover, a closed reaction cycle for the partial oxidation of methane has long been sought, and in achieving this over the Cu-SSZ-13, this study contributes one more step toward identifying a suitable catalyst for direct methane-to-methanol conversion.