Understanding heterogeneous catalysis on an atomic scale: a combined surface science and reactivity investigation for the dehydrogenation of ethylbenzene over iron oxide catalysts

In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe₃O₄(111), -Fe₂O₃(0001) and KFe _x O _y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe₃O₄(111) is catalytically inactive. The catalytic activity of -Fe₂O₃(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.     

Single crystal flow reactor for studying reactivities on metal oxide model catalysts at atmospheric pressure to bridge the pressure gap to the adsorption properties determined under UHV conditions

A flow reactor for the investigation of heterogeneous catalytic reactions on single crystalline metal oxide model catalysts has been designed. It is located in a high pressure cell attached to an UHV analysis chamber where the model catalysts can be prepared and characterized by surface science techniques. It can also be run in a batch modus. After sample transfer the high pressure cell can be completely separated from the UHV chamber and it can be used for oxidation treatments and reaction studies at gas pressures up to 1 bar. A new heating system provides direct heating of the sample by laser light up to 1200 K. Product analysis is done by gas chromatography coupled with mass spectrometry, which allows detection in the ppb range. The single crystal flow reactor provides new insight into the atomic scale surface chemistry of metal oxides under real catalysis conditions and bridges the pressure gap for model systems prepared and characterized under UHV conditions. Results on the dehydrogenation of ethylbenzene to styrene over epitaxial potassium–iron oxide films are presented and correlated to thermal desorption measurements on the same films under UHV conditions.