Lithium Promotes Acetylide Formation on MgO During Methane Coupling Under Non‐Oxidative Conditions

Abstract

A prototypical material for the oxidative coupling of methane (OCM) is Li/MgO, for which Li is known to be essential as a dopant to obtain high C2 selectivities. Herein, Li/MgO is demonstrated to be an effective catalyst for non‐oxidative coupling of methane (NOCM). Moreover, the presence of Li is shown to favor the formation of magnesium acetylide (MgC2), while pure MgO promotes coke formation as evidenced by solid‐state 13C NMR, thus indicating that Li promotes C–C bond formation. Metadynamic simulations of the carbon mobility in MgC2 and Li2C2 at the density functional theory (DFT) level show that carbon easily diffuses as a C2 unit at 1000°C. These insights suggest that the enhanced C2selectivity for Li‐doped MgO is related to the formation of Li and Mg acetylides