The oxidation and reforming kinetics of methane by O2, CO2 and H2O were studied on a stepped Pt(5 5 7) single crystal from 623 to 1050 K under methane rich conditions. The rate of carbon deposition was followed by ex-situ Auger electron spectroscopy under non-oxidative conditions. The apparent activation energy for methane decomposition was significantly lower than the apparent barriers measured for both total oxidation, CO2 and H2O reforming. Total oxidation of methane to CO2 and H2O followed by combined dry and steam reforming (combined combustion-reforming) led to CO production rates which were higher than direct CO2 or H2O reforming rates. The enhanced rates are most likely due to the ability of adsorbed oxygen to prevent carbon nucleation and/or scavenge carbon enabling the reforming reaction to turnover on a larger fraction of sites. Comparable amounts of carbon were found by Auger electron spectroscopy measurements after both direct dry or steam reforming, while combined oxidation-reforming had considerable less carbon. During direct dry or steam reforming, CO2 and H2O serve only to scavenge adsorbed atomic carbon, while in the presence of oxygen, carbon is removed by both combustion and reforming routes.
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