The potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly.

In this Perspective, we highlight the main challenges to be addressed in the development of heterogeneous catalysts for the direct functionalization of methane. Along with our personal view on current developments in this field, we outline the main mechanistic, engineering, and catalyst design issues that have hampered implementation of new technologies and highlight possible paths to overcome these problems.

Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically coupled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemical synthesis method is used to build the microporous MOF matrix while integrating the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the formation of isolated oxobridged Fe units.