Cobalt‐loaded MFI zeolite showed distinct activity for direct methylation of benzene with methane into toluene. High activity was found at around 0.6 of Co/Al molar ratio. Incorporation of carbon from methane into the methyl group of toluene was confirmed with isotope tracer experiments and mass spectroscopy. Ammonia infrared‐mass spectroscopy temperature‐programmed desorption, transmission electron microscopy, X‐ray absorption near edge spectroscopy and extended X‐ray absorption fine structure indicated that Lewis acidic divalent (+II of oxidation state) Co species mono‐atomically dispersed on the ion exchange site of MFI zeolite was the active species.
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