Low‐Temperature, Ambient Pressure Oxidation of Methane to Methanol Over Every Tri‐Iron Node in a Metal–Organic Framework Material

Abstract In contrast with metal‐modified zeolites, metal–organic framework materials (MOFs) provide a platform that may be significantly more amenable to creating catalysts in which every metal site is endowed with the same coordination environment, and hence, catalytic function. Using MIL‐100(Fe) as a prototype, we present the first example of a synthetic heterogeneous catalyst comprised exclusively of active tri‐iron moieties participating in the low‐temperature oxidation of methane to methanol; in contrast with prior reports on iron‐MOFs, we report the near‐exclusive formation of methanol at low temperatures and sub‐ambient methane pressures, and evidence its effectuation solely by Fe 2+ sites. The study captures the utility of exploring classes of materials endowed with a high level of definition in structure and catalytic function for the purposes of overcoming persistent scientific and technological challenges in the field of synthetic heterogeneous catalysis.