Theoretical Insights into Dual-Metal-Site Catalysts for the Nonoxidative Coupling of Methane

Abstract

Direct conversion of methane to C2 hydrocarbons under nonoxidative conditions is an attractive technology but is challenging due to high reaction temperature, severe coke deposition, and low selectivity. Here, we report three dual-metal-site catalysts (DMSCs) based on nitrogen-doped graphene (FeCo–N–C, Fe2–N–C, and Co2–N–C) for nonoxidative coupling of methane to C2 hydrocarbons from a theoretical perspective. Our calculated results reveal that DMSCs present universally better performance in methane activation than single-metal-site catalysts (Fe–N–C and Co–N–C). Among the three DMSCs, Co2–N–C exhibits the best catalytic activity and superior selectivity to ethane in the whole reaction pathway. Our microkinetic modeling reveals that the Co2–N–C catalyst can convert methane to CH3, C2H6, and H2 at 1200 K. The electronic structure analysis and ab initio molecular dynamics simulations demonstrate that Co2–N–C possesses both intrinsic stability and high-temperature stability. Moreover, Co2–N–C also manifests better coke resistance compared with larger Co clusters, indicated by the difficult kinetics of methane deep dehydrogenation to naked carbon. This work provides a potential catalyst prototype for the selective conversion of methane to C2 hydrocarbons under nonoxidative conditions.