Structural Single Fe(II) Sites in MIL-Type Metal Or-Ganic Frameworks for Oxidation of Methane to Methanol and Ethane to Ethanol

Single non-heme Fe(II) ions present as structural metals in several metal organic frameworks (e.g. MIL-100, MIL-101, MIL-808) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol<sup>-1</sup> for ethane and 60 kJ mol<sup>-1</sup> for methane following oxidative activation of iron. Through consideration of the full reaction profile leading to the corresponding alcohols ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stability of these MOFs together with the scalability of their syntheses make them attractive catalysts for the selective low temperature conversion of light alkanes to higher-value oxygenates.