In-situ investigation of gas phase radical chemistry in the catalytic partial oxidation of methane on Pt

The catalytic partial oxidation of methane on platinum was studied in situ under atmospheric pressure and temperatures between 1000 and 1300 °C. By combining radical measurements using a molecular beam mass spectrometer and threshold ionization with GC, GC–MS and temperature profile measurements it was demonstrated that a homogeneous reaction pathway is opened at temperatures above 1100 °C, in parallel to heterogeneous reactions which start already at 600 °C. Before ignition of gas phase chemistry, only CO, H2, CO2 and H2O are formed at the catalyst surface. Upon ignition of gas chemistry, CH3radical dot radicals, C2 coupling products and traces of C3 and C4 hydrocarbons are observed. Because the formation of CH3radical dot radicals correlates with the formation of C2 products it can be concluded that C2 products are formed by coupling of methyl radicals in the gas phase followed by dehydrogenation reactions. This formation pathway was predicted by numerical simulations and this work presents an experimental confirmation under high temperature atmospheric pressure conditions.