Interactions of methane and carbon monoxide with platinum - Supported catalysts and chemical sensors

Abstract: This thesis aims at increasing the understanding of the interactions of methane and carbon monoxide with platinum in connection to catalysis and sensor technology for emission control. Specifically, the low-temperature oxidation of methane and carbon monoxide over supported platinum catalysts and the sensor response mechanism towards CO of platinum-based chemical field effect sensors were studied. Flow-reactor experiments and in situ spectroscopic methods (mainly FTIR and energy dispersive XAS) in combination with mass spectrometry were employed at both steady-state and transient reaction conditions. The results show that the support material for platinum has a considerable impact on the low-temperature activity for oxidation of both CO and methane in oxygen excess. Under such conditions methane oxidation over platinum is generally low due to oxygen-poisoning, hindering the dissociative adsorption of methane. However, by employing transient operation of the feed-gas composition, the activity for methane oxidation can be substantially increased. A new method was developed and applied for analysis of in situ XAS spectra. It was found that transient operation of the feed-gas affects the surface composition of reactants and the state of the catalyst surface. At low temperatures, the CO oxidation reaction often suffers from self-poisoning by carbon monoxide. By supplying oxygen to the reaction through alternative routes, e.g. via additional compounds or via the support material, the low-temperature activity for CO oxidation can be significantly increased. Further, the CO coverage and the reduction of oxygen from the surface of platinum-based field effect sensors were found to be important factors in the sensing mechanism towards carbon monoxide of such devices.