Exploring the Methane to Methanol Oxidation over Iron and Copper Sites in Metal–Organic Frameworks

The direct oxidation of methane to methanol (MTM) is a significant challenge in catalysis and holds profound economic implications for the modern chemical industry. Bioinspired metal–organic frameworks (MOFs) with active iron and copper sites have emerged as innovative catalytic platforms capable of facilitating MTM conversion under mild conditions. This review discusses the current state of the art in applying MOFs with iron and copper catalytic centers to effectuate the MTM reaction, with a focus on the diverse spectroscopic techniques employed to uncover the electronic and structural properties of MOF catalysts at a microscopic level. We explore the synthetic strategies employed to incorporate iron and copper sites into various MOF topologies and explore the efficiency and selectivity of the MOFs embedded with iron and copper in acting as catalysts, as well as the ensuing MTM reaction mechanisms based on spectroscopic characterizations supported by theory. In particular, we show how integrating complementary spectroscopic tools that probe varying regions of the electromagnetic spectrum can be exceptionally conducive to achieving a comprehensive understanding of the crucial reaction pathways and intermediates. Finally, we provide a critical perspective on future directions to advance the use of MOFs to accomplish the MTM reaction.