Revealing the Synergetic Effects between Reactants in Oxidative Coupling of Methane on Stepped MgO(100) Catalyst

Abstract

The oxidative coupling of methane (OCM) on MgO is often computationally explored via Mars-Krevelen (MvK) mechanism. However, the difficult desorption of CH3 radical at stepped MgO surface shadow the feasibility of mechanism. In this work, density functional theory calculations are performed to unravel the syngenetic effects between reactants which lead to a new Langmuir-Hinshelwood (L-H)-like mechanism. It was found that co-adsorption of reactants pave ways for CH3 radical formation with negligible desorption energy. The role of oxygen molecule is not only to oxidize reduced surface but also decrease the reactivity of Mg-O site which facile CH3 desorption. Electronic structure analysis indicated the distinct feature along pathway between MvK and L-H. The current work clearly indicated the importance of effective interactions between reactants and provided new insights on the reaction mechanism of OCM.