CHEMISORPTION OF ETHYLENE AND ACETYLENE ON ULTRATHIN PD FILMS ON MO(100)

Previous studies of the chemisorption properties of ultrathin (mono-, bi-, and trilayer) metal films have usually focused on CO adsorption. While the CO adsorption energy on these Pd films is often decreased, C O is one of the strongest pi-acceptor ligands and probes mainly one as pect of the chemistry of these surfaces. We report here the first deta iled study on ultrathin metal films of the chemisorption of two unsatu rated hydrocarbons, C2H4 and C2H2, which initially bond to the surface as sigma-donors and can rehybridize to form strong metal-carbon bonds . The adsorption and dehydrogenation of ethylene and acetylene on mono layer and ultrathin Pd films on Mo(100) were investigated using Auger electron spectroscopy (AES), temperature-programmed desorption (TPD), and high-resolution electron energy loss spectroscopy (HREELS). The ps eudomorphic monolayer of Pd on Mo(100) has greatly altered chemisorpti on properties for C2H4. Ethylene is weakly chemisorbed on the Pd monol ayer, and the adsorbed species is much less rehybridized from sp2 in t he gas phase toward sp3 on this surface compared to C2H4 chemisorbed o n the (100) surface of bulk Pd. In addition, a smaller fraction of the adsorbed ethylene dehydrogenates during TPD experiments on the Pd mon olayer compared to thicker Pd films; i.e., the selectivity for reversi ble C2H4 adsorption is increased on the Pd monolayer. The weaker C2H4 chemisorption interaction of the Pd monolayer is consistent with previ ous CO adsorption studies, along with UV photoemission studies and ele ctronic structure calculations showing a filled d-band. However, acety lene chemisorption is not affected like C2H4, and C2H2 is strongly reh ybridized from sp in the gas phase toward sp3 on the Pd monolayer as i t is on bulk Pd(100). We propose that the C2H2-Pd interaction is stron g enough to rehybridize Pd in the monolayer back toward its normal bul k electronic structure (with a partially filled d-band) in order to ha ve the favorable energy change from a large heat of adsorption for C2H 2 and strong Pd-C bonding.