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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 4669-4684 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Combining molecular beam techniques and time-resolved infrared reflection absorption spectroscopy (TR-IRAS) we have studied the kinetics of the CO oxidation reaction on an alumina-supported Pd model catalyst. The Pd particles are deposited by metal evaporation under ultrahigh vacuum (UHV) conditions onto a well-ordered alumina film, prepared on a NiAl(110) single crystal. Particle size, density and structure of the Pd deposits have been characterized in previous studies. In the low temperature region, transient and steady-state experiments have been performed over a wide range of CO and oxygen fluxes by crossing two effusive molecular beams on the sample surface. We determine the steady-state CO2 production rate as a function of the CO fraction in the impinging gas flux. Simultaneously, the occupation of CO adsorption sites under steady-state conditions is monitored by in situ IR spectroscopy. The origin of different types of CO2 transients is discussed. In particular we focus on the transient CO2 production after switching off the CO beam. For the model catalyst investigated, detailed reaction rate measurements in combination with time-resolved IRAS show that the origin of the particular transient behavior of the supported model system is not due to the presence of specific adsorption sites on small particles, as has been proposed previously. Instead, we show that the transient behavior can be semiquantitatively simulated on the basis of a simple kinetic model considering a homogeneous surface, and accounting for the inhibition of the dissociative adsorption of O2 at high CO coverage. Moreover, it is discussed how the inherent heterogeneity of the supported particle system can additionally enhance the observed effect. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1522-1530 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have studied the collision-induced desorption (CID) of hydrocarbons physisorbed on Au(111). Adsorbed layers of benzene, toluene, deuterated toluene, and n-alkanes of various chainlengths (CnH2n+2, n=5,7,10,12) were exposed to a beam of hyperthermal Xe generated in a supersonic expansion. Adsorbate coverages and their evolution were detected using He atom reflectivity. The CID cross-sections and threshold energies were determined for Xe translational energies in the range of 1.6–5.8 eV. According to their desorption behavior the physisorbed hydrocarbons can be assigned to two categories. "Rigid" aromatic molecules, such as benzene and toluene, show large CID cross sections. The ratios between the CID threshold energies and the desorption energies as determined from TPD (temperature programmed desorption) experiments can be understood within the simple hard sphere–cube (HSC) collision model. For the "flexible" n-alkanes a strong chain-length-dependent reduction of the CID cross sections is found, whereas the desorption thresholds are shifted to higher energies and appear to be directly proportional to the corresponding desorption energies. These effects are tentatively assigned to the excitation of internal degrees of freedom for the latter group of adsorbates, for which only a fraction of the atoms composing the molecule is involved in the initial collisional energy transfer. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 71 (2000), S. 4395-4408 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: We describe a newly developed ultrahigh vacuum (UHV) experiment which combines molecular beam techniques and in situ surface spectroscopy. It has been specifically designed to study the reaction kinetics and dynamics on complex model catalysts. The UHV system contains: (a) a preparation compartment providing the experimental techniques which are required to prepare and characterize single-crystal based model catalysts such as ordered oxide surfaces or oxide supported metal particles; and (b) the actual scattering chamber, where up to three molecular beams can be crossed on the sample surface. Two beams are produced by newly developed differentially pumped sources based on multichannel arrays. The latter are capable of providing high intensity and purity beams and can be modulated by means of a vacuum-motor driven and computer-controlled chopper. The third beam is generated in a continuous or pulsed supersonic expansion and is modulated via a variable duty-cycle chopper. Angular and time-resolved measurements of desorbing and scattered molecules are performed with a rotatable doubly differentially pumped quadrupole mass spectrometer with a liquid-nitrogen cooled ionizer housing. Time-resolved but angle-integrated measurements are realized with a second nondifferentially pumped quadrupole mass spectrometer. In situ measurements of adsorbed species under reaction conditions are performed by means of an adapted vacuum Fourier transform infrared spectrometer. The spectrometer provides the possibility of time-resolved measurements and can be synchronized with any of the beam sources. This contribution provides a general overview of the system and a description of all new components and their interplay. We also present test data for all components employing simple adsorption/desorption and reaction systems. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Surface Science 307-309 (1994), S. 1148-1160 
    ISSN: 0039-6028
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Surface Science 318 (1994), S. 61-73 
    ISSN: 0039-6028
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Surface Science 315 (1994), S. L977-L982 
    ISSN: 0039-6028
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Electron Spectroscopy and Related Phenomena 64-65 (1993), S. 217-225 
    ISSN: 0368-2048
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Electron Spectroscopy and Related Phenomena 68 (1994), S. 347-355 
    ISSN: 0368-2048
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1572-879X
    Keywords: aluminum oxide ; hydroxyl groups ; rhodium ; growth ; scanning tunneling microscopy ; infrared spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to investigate how the presence of surface hydroxyl groups on oxide surfaces affects the interaction with the supported metal, we have modified a well-ordered alumina film on NiAl(110) by Al deposition and subsequent exposure to water. This procedure yields a hydroxylated alumina surface as revealed by infrared and high-resolution electron energy loss spectroscopy. By means of scanning tunneling microscopy, we have studied the growth of rhodium on the modified film at 300 K. Clear differences in the particle distribution and density are observed in comparison to the clean substrate. While, in the latter case, decoration of domain boundaries as typical defects of the oxide film governs the growth mode, a more isotropic island distribution and a drastically increased particle density is found on the hydroxylated surface. From infrared data, it can be deduced that the growth is connected with the consumption of the hydroxyl groups due to the interaction between the metal deposit and the hydroxylated areas. This finding is in line with photoemission results published earlier.
    Type of Medium: Electronic Resource
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