Beyond Radical Rebound: Methane Oxidation to Methanol Catalyzed by Iron Species in Metal-Organic Framework Nodes

Recent work has exploited the ability of metal-organic frameworks (MOFs) to isolate Fe sites that mimic the structures of sites in enzymes that catalyze selective oxidations at low temperatures, opening new pathways for the valorization of underutilized feedstocks such as methane. Questions remain as to whether the radical-rebound mechanism commonly invoked in enzymatic and homogeneous systems also applies in these rigid-framework materials, in which resisting the overoxidation of desired products is a major challenge. We demonstrate that MOFs bearing Fe(II) sites within Fe₃-μ₃-oxo nodes active for conversion of CH₄ + N₂O mixtures (368-408 K) require steps beyond the radical-rebound mechanism to protect the desired CH₃OH product. Infrared spectra and density functional theory show that CH₃OH_(g) is stabilized as Fe(III)-OCH₃ groups on the MOF via hydrogen atom transfer with Fe(III)-OH groups, eliminating water. Consequently, upon addition of a protonic zeolite in inter- and intrapellet mixtures with the MOF, we observed increases in CH₃OH selectivity with increasing ratio and proximity of zeolitic H⁺ to MOF-based Fe(II) sites, as methanol is protected within the zeolite. We infer from the data that CH₃OH_(g) is formed via the radical-rebound mechanism on Fe(II) sites but that subsequent transport and dehydration steps are required to protect CH₃OH_(g) from overoxidation. The results demonstrate that the radical-rebound mechanism commonly invoked in this chemistry is insufficient to explain the reactivity of these systems, that the selectivity-controlling steps involve both chemical and physical rate phenomena, as well as offering a strategy to mitigate overoxidation in these and similar systems.