Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single‐Atom Catalysts

The direct, nonoxidative conversion of methane on a silica‐confined single‐atom iron catalyst is a landmark discovery in catalysis, but the proposed gas‐phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe1©SiC2), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH2 intermediate. We find a quasi Mars–van Krevelen (quasi‐MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe1©SiO2 and this surface process is identified to be more plausible than the alternative gas‐phase reaction mechanism. A quasi Mars–van Krevelen surface reaction mechanism involving withdrawal and regenerating surface carbon atom during nonoxidative catalytic conversion of methane on Fe1©SiC2 is presented.