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, CO 2, and C 2 H 2; C 2 H 2 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-σ configuration, while on monolayer Pd(111)/Mo(110), the maleic anhydride is bonded to the surface through the olefin via a π-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 ∼150 cm -1 on the monolayer Pd(111)/Mo(110) surface, unshifted on the multilayer Pd(111)/Mo(110) surface, and blue-shifted by ∼100 cm -1 on the Mo(110) surface.