Abstract

The reaction pathways of cis- and trans-2-butene on clean Mo(110) and carbide-modified Mo(110) surfaces have been studied using a combination of temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The vibrational data reveal that the decomposition pathways of cis- and trans-2-butene are different on clean Mo(110). In the case of cis-2-butene, the olefinic α(C–H) bonds are cleaved at 80 K to produce surface hydrogen and 2-butyne. In contrast, the initial decomposition of trans-2-butene also involves β(C–H) bond scission, such that at least one of the methyl groups of the molecule is converted to a CH 2 group at temperatures below 150 K. On carbide-modified Mo(110), the initial decomposition step for both cis- and trans-2-butene involves α(C–H) bond cleavage to form 2-butyne. This difference in reactivity of Mo(110) and carbide-modified Mo(110) towards the 2-butenes provides experimental evidence that the formation of the carbide overlayer enhances the selective activation of α(C–H) bonds.

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