Bioinspired Metal–Organic Framework Catalysts for Selective Methane Oxidation to Methanol

Particulate
methane monooxygenase (pMMO) is an enzyme that oxidizes
methane to methanol with high activity and selectivity. Limited success
has been achieved in incorporating biologically relevant ligands for
the formation of such active site in a synthetic system. Here, we
report the design and synthesis of metal–organic framework
(MOF) catalysts inspired by pMMO for selective methane oxidation to
methanol. By judicious selection of a framework with appropriate topology
and chemical functionality, MOF-808 was used to postsynthetically
install ligands bearing imidazole units for subsequent metalation
with Cu­(I) in the presence of dioxygen. The catalysts show high selectivity
for methane oxidation to methanol under isothermal conditions at 150
°C. Combined spectroscopies and density functional theory calculations
suggest bis­(μ-oxo) dicopper species as probable active site
of the catalysts.