Mixed Anion Control of the Partial Oxidation of Methane to Methanol on the β-PtO(2) Surface

[Image: see text] Although the C–H bond of methane is very strong, it can be easily dissociated on the (110) surface of β-PtO(2). This is because a very stable Pt–C bond is formed between the coordinatively unsaturated Pt atom and CH(3) on the surface. Owing to the stable nature of the Pt–C bond, CH(3) is strongly bound to the surface. When it comes to methanol synthesis from methane, the Pt–C bond has to be cleaved to form a C–O bond during the reaction process. However, this is unlikely to occur on the β-PtO(2) surface: The activation energy of the process is calculated to be so large as 47.9 kcal/mol. If the surface can be modified in such a way that the ability for the C–H bond activation is maintained but the Pt–C bond is weakened, a catalyst combining the functions of C–H bond cleavage and C–O bond formation can be created. For this purpose, analyzing the orbital interactions on the surface is found to be very useful, resulting in a prediction that the Pt–C bond can be weakened by replacing the O atom trans to the C atom with a N atom. This would be a sort of process to make β-PtO(2) a mixed anion compound. Density functional theory simulations of catalytic reactions on the β-PtO(2) surface show that the activation energy of the rate-limiting step of methanol synthesis can be reduced to 27.7 kcal/mol by doping the surface with N.