Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site

Abstract

Natural gas, consisting mainly of methane (CH₄), has a relatively low energy density at ambient conditions (~36 kJ l^-1). Partial oxidation of CH₄ to methanol (CH₃OH) lifts the energy density to ~17 MJ l^-1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C-H bond in CH₄ (439 kJ mol^-1) and facile over-oxidation of CH₃OH to CO and CO₂. Here we report the direct photo-oxidation of CH₄ over mono-iron hydroxyl sites immobilized within a metal-organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H₂O and O₂, CH₄ is converted to CH₃OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol g_cat^-1 h^-1 (versus 5.05 mmol g_cat^-1 h^-1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH₄ by forming an [Fe-OH···CH₄] intermediate, thus lowering the barrier for C-H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C-H bond activation in CH₄ to drive the direct photosynthesis of CH₃OH.