Ethene adsorption, dehydrogenation and reaction with Pd(110): Pd as a carbon 'sponge'

The interaction of ethene with the Pd(110) surface has been investigated, mainly with a view to understanding the dehydrogenation reactions of the molecule and mainly using a molecular beam reactor. Ethene adsorbs with a high probability over the temperature range 130 to 800 K with the low-coverage sticking probability dropping from 0.8 at 130 K to 0.35 at 800 K. The adsorption is of the precursor type, with a weakly held form of ethene being the intermediate between the gas phase and strong chemisorption. Dehydrogenation begins at similar to300 K and is fast above 350 K. If adsorption is carried out at temperatures up to similar to380 K, adsorption saturates after about 0.25 monolayer have adsorbed, but above similar to450 K, adsorption continues at a high rate with continuous hydrogen evolution and C deposition onto the surface. It appears that, in the intermediate temperature range, the carbonaceous species formed is located in the top layer and thus interferes with adsorption, whereas the C goes subsurface above 450 K, the adsorption is almost unaffected, and the C signal is significantly attenuated in XPS. However, the deposited carbon can easily be removed again by reaction with oxygen, thus implying that the carbon remains in the selvedge, that is, in the immediate subsurface region probably consisting of a few atomic layers. No well-ordered structures are identified in either LEED or STM, though some evidence of a c(2x2) structure can be seen. The Pd surface, at least above 450 K, appears to act as a sponge for carbon atoms, and this effect is also seen for the adsorption of other hydrocarbons such as acetaldehyde and acetic acid.