Single-Step Selective Oxidation of Methane by Iron-Oxo Species in the Metal–Organic Framework MFU-4l

The direct and selective conversion of methane to methanol can be considered a holy grail for catalysis research. In this work, we study a metal-organic framework known as MFU-4l, modified by design to include highly reactive iron-oxo species for the catalytic C-H bond activation of methane. We investigate the oxidation of methane and the further potential oxidation of the product methanol using N₂O as an oxygen source and map the potential energy landscape of these reactions using density functional theory calculations. We show that the highest energy barrier encountered during the methane oxidation process is not the C-H bond breaking, but the activation of the iron center by N₂O. Furthermore, the potential energy landscape for the C-H bond activation exhibits a large, high-energy plateau region instead of a sharp transition state, thus differing from the traditional radical rebound mechanism. This insight offers interesting potential routes to enhance the catalytic activity of the catalyst, to hinder unwanted deactivation pathways, and to reduce the activity towards the over-oxidation of the product.