Theoretical Study on the C-H Activation of Methane by Liquid Metal Indium: Catalytic Activity of Small Indium Clusters.

The mechanism of C-H activation of methane by liquid indium, which is the first step of the dehydrogenative conversion of methane to higher hydrocarbons, was investigated using density functional theory calculations. In the first-principle molecular dynamics trajectory at the experimental temperature (1200 K), low-coordinated indium atoms continuously appear on the disordered liquid surface. The C-H cleavage is endothermic on clean surfaces, while the low-coordinated indium atoms reduce the endothermicity significantly. In small indium clusters, which are models of low-coordinated atoms on a surface, the calculated activation energy is much smaller than that on the clean surface. The energy level of the methane C-H σ* orbital is reduced by the interaction with the indium 5pσ orbitals. In2 shows the lowest activation energy and exothermicity in the C-H bond cleavage.