Theoretical study of the reaction mechanism of platinum oxide with methane

Density functional B3LYP calculations have been employed to investigate the reaction of platinum oxide with methane. PtO is shown to form a molecular complex with CH4 bound by ∼13 kcal/mol. At elevated temperatures, direct abstraction of a hydrogen atom is possible leading to PtOH and free methyl radical with a barrier of ∼26 kcal/mol. A minor reaction channel is insertion into a C–H bond to produce a CH3PtOH molecule, which can be also formed by recombination of PtOH and CH3. CH3PtOH would preferably dissociates through a mechanism involving 1,2-CH3 migration to produce a PtCH3OH complex and eventually Pt+CH3OH.