LEED,AES and thermal desorption studies of chemisorbed Hydrogen and hydrocarbons (C2H2, C2H4, C6H6, C6H12) on the (111) and stepped [6(111) × (100)] iridium crystal surfaces; comparison with platinum

The adsorption of hydrogen, ethylene, acetylene, cyclohexane and benzene was studied on both the (111) and stepped 6(111) × (100)] crystal surfaces of iridium. The techniques used were low energy electron diffraction, Auger electron spectroscopy, and thermal desorption mass spectrometry. At 30°C, acetylene, ethylene and benzene are adsorbed with a sticking probability near unity. The sticking probability of cyclohexane is less than 0.1 on both surfaces. Heating the (111) surface above 800°C, in the presence of the hydrocarbons, results in the formation of an ordered carbonaceous overlayer with a diffraction pattern corresponding to a (9 × 9) surface structure. No indication for ordering of the carbonaceous residue was found on the stepped iridium surface in these experimental conditions. The hydrocarbon molecules form only poorly ordered surface structures on both iridium surfaces when the adsorption is carried out at 30°C. Benzene is the only gas that can be desorbed from the surfaces in large amounts by heating. Ethylene remains largely on the surface, only a few percent is removed by heating while acetylene and cyclohexane cannot be desorbed at all. When adsorption is carried out at 30°C and the crystal is subsequently flashed to high temperature, hydrogen is liberated from the surface. The hydrogen desorption spectra from the iridium surfaces exposed to C₂H₄, C₂H₂, or C₆H₆ exhibit two hydrogen desorption peaks, one around 200°C and the second around 350°C. The temperatures where these peaks appear vary slightly with the type of hydrocarbon. The relative intensities of these two peaks depend strongly on the surface used. Arguments are presented that decomposition of the hydrocarbon molecules (C-H bond breaking nd possibly also C-C bond breaking) occurs easier on the stepped iridium surface than on the (111) surface. Hydrogen is desorbed at a higher temperature from an iridium surface possessing a high density of surface imperfections than from a perfect iridium (111) surface. The results are compared with those obtained previously on similar crystal surfaces of platinum. It appears that C-H bond breaking occurs more easily on iridium than on platinum.