Activation of methane over supported metal catalysts was investigated using MS-pulse technique on-line. Oxygen-free CH4 pulsing reactions were carried out over both Rh/SiO2 and Ru/SiO2 at 700 degreesC. Large amounts of CO and CO2 were observed at the first pulse of CH4 over oxidized Rh(O)/SiO2 catalyst. However, no CO2 formation was observed at the second pulse and thereafter. Similar to the response of Rh(O) /SiO2 catalyst, the intensity of CO and CO2 was strong at the first pulse over reduced Rh/SiO2 catalyst, and CO2 appeared also only at the first pulse over Rh/SiO2 catalyst. No CO2 was detected at the second pulse and thereafter. CH4 pulsing over Ru(O)/SiO2 catalyst also produced CO and CO2. CO and CO2 were detected from the first pulse I and their intensity was much stronger than that of CO and CO2 produced over Rh/SiO2 catalyst. However, unlike Rh/SiO2 catalyst, CO2 was formed at every pulse over Ru(O)/SiO2 catalyst. Pulsing CH4 over Ru/SiO2 catalyst also produced both CO and CO2 at every pulse. This difference between Rh and Ru catalysts may be due to the difference in the bond strength of Ru-O (528.4 kJ/mol) and Rh-O (405.1 kJ/mol) and in their relative oxygen affinities, Ru-0 can be more easily oxidized by O-2 than Rh-0 owing to the greater oxygen affinity of Ru. Surface oxygen should play an important role in the activation of methane and the product distribution
