Langmuir, Vol.12, No.7, 1807-1816, 1996
Adsorption and Reaction of Maleic-Anhydride on Mo(110), Monolayer Pd(111)/Mo(110), and Multilayer Pd(111)Mo(110)
The adsorption and reaction of maleic anhydride and deuterated maleic anhydride on Mo(110), monolayer Pd/Mo(110), and multilayer Pd(111)/Mo(110) surfaces have been studied using temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Maleic anhydride adsorbs irreversibly on the Mo(110) surface at 100 K. Heating to 1200 K yields adsorbed carbon (C-ads) and gas-phase CO and H-2. In contrast, the adsorption of maleic anhydride on monolayer Pd(111)/Mo(110) and multilayer Pd(111)/Mo(110) surfaces is largely reversible with the chemisorbed maleic anhydride desorbing at 365 and 375 K, respectively. Approximately 15% of the chemisorbed maleic anhydride decomposes upon heating to 400 K, forming CO, CO2, and C2H2; C2H2 further dehydrogenates upon heating to C-ads and gas-phase H-2. The HREELS measurements indicate that maleic anhydride is bonded to multilayer Pd(111)/Mo(110) through the olefin bond in a di-sigma configuration, while on monolayer Pd(111)/Mo(110), the maleic anhydride is bonded to the surface through the olefin via a pi-bond. On the Mo(110) surface, maleic anhydride is bonded to the surface through the ring oxygen with the molecular plane perpendicular to the surface. As a result of this modified adsorption geometry, the carbonyl stretching mode is red-shifted similar to 150 cm(-1) on the monolayer Pd(111)/Mo(110) surface, unshifted on the multilayer Pd(111)/Mo(110) surface, and blue-shifted by similar to 100 cm(-1) on the Mo(110) surface.
Keywords:ULTRATHIN PD FILMS;ELECTRONIC-STRUCTURE;CARBON-MONOXIDE;THIN-FILMS;SURFACE;CHEMISORPTION;TEMPERATURE;ACETYLENE;ETHYLENE;MO(100)