I present a molecular beam study of methane dissociation on differ-ent surface sites of several platinum single crystal surfaces (Pt(111), Pt(211), Pt(210), Pt(110)-(2x1)). The experiments were performed in a molecular beam/surface-science apparatus that combines rovibrational state-selective excitation of reactants with detection of the reaction products by reflection absorption infrared spectroscopy (RAIRS), Auger electron spectroscopy (AES) and King and Wells (K&W) technique. First, I explore how the barrier for methane dissociation depends on the Pt surface site (terrace, step, kink, and ridge atoms). For that, I compare the average reaction probabilities of methane on the different crystals using K&W. Moreover, I used the site-specific detection of chemisorbed methyl species by RAIRS to obtain the site-specific reactivity on steps, ridges and terraces. The highest methane reactivity and therefore the lowest barrier was observed for the surface atoms with the lowest coordination. The trans-lational energy dependence of the reactivity shows clear evidence for a direct activated mechanism on all the surface sites studied. The decreasing catalyt-ic activity for Pt atoms with increasing coordination number agrees well with theoretical predictions using first principles quantum theory calculations. Second, I present the role of rovibrational excitation of the incident methane on the chemisorption on different surface sites. For CH4, excitation of one quantum of the antisymmetric C-H stretch vibration (Îœ3) was found to be less efficient than an equivalent amount of translational energy normal to the sur-face for promoting the dissociation on all the surface sites. The vibrational efficacy was seen to be lower for dissociation on the low coordinated sites, in accordance with calculations of transition state geometries. For CH3D, the excitation of the antisymmetric C-H stretch vibration (Îœ4) led to bond selec-tivity on the steps and terraces of the Pt(211) surface. These results show how careful control of the translational energy and rovibrational state of the incident CH3D can be used for site-specific and bond-selective dissociation of methane. As predicted previously by theory but not observed before experi-mentally, the C-H bond selectivity is shown to decrease with increasing translational energy. Third, I explore the effect of surface temperature on the methane dissocia-tion. The sticking coefficient for a direct chemisorption reaction such as CH4 on Pt, might be expected to be independent of surface temperature, because the reaction happens very fast leaving very little time for the molecule to equilibrate with the surface. However, I observed an increase in methane reactivity with increasing surface temperature at low incident CH4 energies. This observation is interpreted by a âloss of coordinationâ from the atoms displaced out of the plane due to their vibrational motion when the surface is heated. The surface-site and quantum-state-specific data presented in this thesis are ideally suitable for testing theoretical models that aim to describe the me-thane-surface reaction at the microscopic level. Moreover, the characteriza-tion of different catalytically active sites for methane dissociation contrib-utes to advancing the understanding of methane reactivity towards real cata-lytic conditions, where surfaces with several different atomic terminations are used.
EPFL2019
