Journal of Physical Chemistry B, Vol.101, No.20, 4044-4054, 1997
Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy
The bonding and reactivity of benzene on carbide-modified Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD) to investigate the effects of carbide formation on the chemistry of this early transition metal surface. For comparison, the reactions of benzene with both clean Mo(110) and oxygen-modified Mo(110) surfaces have been studied as well. We find that benzene adsorbs on all three types of surfaces at 80 K with the molecular plane parallel to the surface. For the case of benzene adsorption on the oxygen-modified surface, the similarity between the vibrational frequencies observed in the HREELS spectrum and infrared spectrum of liquid benzene indicates that benzene interacts only weakly with this surface. On the clean Mo(110) surface, the HREELS data show that adsorption occurs on only one type of surface site, and the benzene layer is stable to at least 325 K. Between 325 and 350 K, benzene decomposes to form benzyne, as proposed earlier by Liu et al. Finally, for the carbide-modified surface, it is observed that the benzene decomposes above similar to 350 K to produce CxHy fragments. The latter reactivity is similar to what is observed for benzene on the platinum group metals, especially on Rh(111).
Keywords:ENERGY LOSS SPECTROSCOPY;CRYSTAL-SURFACES;CARBON-MONOXIDE;THERMAL-DECOMPOSITION;ELECTRONIC-STRUCTURE;SINGLE-CRYSTALS;PLATINUM;HYDROCARBONS;DISSOCIATION;REACTIVITY