Approaches for Selective Oxidation of Methane to Methanol

Abstract

Methane activation chemistry, despite being widely reported in literature, remains to date a subject of debate. The challenges in this reaction are not limited to methane activation but extend to stabilization of the intermediate species. The low C-H dissociation energy of intermediates vs. reactants leads to CO2 formation. For selective oxidation, nature presents methane monooxygenase as a benchmark. This enzyme selectively consumes methane by breaking it down into methanol. To assemble an active site similar to monooxygenase, the literature reports Cu-ZSM-5, Fe-ZSM-5, and Cu-MOR, using zeolites and systems like CeO2/Cu2O/Cu. However, the trade-off between methane activation and methanol selectivity remains a challenge. Density functional theory (DFT) calculations and spectroscopic studies indicate catalyst reducibility, oxygen mobility, and water as co-feed as primary factors that can assist in enabling higher selectivity. The use of chemical looping can further improve selectivity. However, in all systems, improvements in productivity per cycle are required in order to meet the economical/industrial standards.