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.

Impregnation of various heteroelements on the ZSM-5 zeolite was applied to improvement of the catalytic activity in toluene disproportionation. Nickel loaded on ZSM-5 (Ni/ZSM-5) exhibited higher catalytic activity (toluene conversion) and lower benzene / xylene ratio (closer to the stoichiometry, meaning low rate of side reaction) than H-ZSM-5 zeolite. The Ni/ZSM-5 with Ni/Al = 0.6 showed the maximum in catalytic activity, and excess Ni loading caused decrease in the conversion and increase in the benzene / xylene ratio due to decrease of acid amount and acceleration of dealkylation, respectively. The detailed analysis of acidic property by means of 2 ammonia IRMS-TPD method showed that the Ni loading generated Lewis acid sites on the zeolite. The synergy of Brønsted and Lewis acid sites, ascribed to Si-OH-Al and Ni species, respectively, is suggested to give the high activity of desired reaction.