R. Denecke

New setup for in situ x-ray photoelectron spectroscopy from ultrahigh vacuum to 1 mbar

In an effort to extend the pressure range for electron-based spectroscopies from ultrahigh vacuum into the so-called pressure gap region, we have built a new apparatus for in situ x-ray photoelectron spectroscopy up to 1mbar. The principle of the experimental setup is based on a modified hemispherical electron energy analyzer, a modified twin anode x-ray source, and several differential-pumping stages between sample region and electron detection. The reaction gas is provided in situ either by background dosing or, as a new feature, by beam dosing, using a directed gas beam from a small tube. The latter allows for higher local pressures. The performance of the new setup is discussed, deriving normalization procedures from the analysis of the attenuation of the substrate photoemission intensity by the increasing gas phase pressure. In addition, the change of the work function due to changes in surface composition can be evaluated in situ by analyzing the binding energy shift of the gas phase core-level peak...

Kinetic parameters of CO adsorbed on Pt(111) studied by in situ high resolution x-ray photoelectron spectroscopy

The kinetics of the adsorption system CO/Pt(111) has been studied by time-resolved high-resolution x-ray photoelectron spectroscopy using third generation synchrotron radiation at BESSY II. CO is dosed by a supersonic molecular beam device which allows for a high sample pressure (here up to 10−6 mbar) and a fast switching of the pressure. The site-specific occupation of CO adsorbed on on-top and bridge sites is determined quantitatively from C 1s spectra, which can be taken with a minimum collection time of 1.5 s per spectrum. Based on the observation of thermal equilibrium between the two sites, we perform a phenomenological analysis of the data, assuming a constant binding energy difference ΔE. From the on-top/bridge occupation ratio as a function of coverage obtained by uptake measurements we extract a value of ΔE=41 meV. With the same ansatz, ΔE is calculated from temperature-dependent measurements at a constant coverage. Finally, determination of the coverage during isothermal desorption is used to o...

Microscopic models of PdZn alloy catalysts: structure and reactivity in methanol decomposition

We review systematic experimental and theoretical efforts that explored formation, structure and reactivity of PdZn catalysts for methanol steam reforming, a material recently proposed to be superior to the industrially used Cu based catalysts. Experimentally, ordered surface alloys with a Pd : Zn ratio of approximately 1 : 1 were prepared by deposition of thin Zn layers on a Pd(111) surface and characterized by photoelectron spectroscopy and low-energy electron diffraction. The valence band spectrum of the PdZn alloy resembles closely the spectrum of Cu(111), in good agreement with the calculated density of states for a PdZn alloy of 1 : 1 stoichiometry. Among the issues studied with the help of density functional calculations are surface structure and stability of PdZn alloys and effects of Zn segregation in them, and the nature of the most likely water-related surface species present under the conditions of methanol steam reforming. Furthermore, a series of elementary reactions starting with the decomposition of methoxide, CH(3)O, along both C-H and C-O bond scission channels, on various surfaces of the 1 : 1 PdZn alloy [planar (111), (100) and stepped (221)] were quantified in detail thermodynamically and kinetically in comparison with the corresponding reactions on the surfaces Pd(111) and Cu(111). The overall surface reactivity of PdZn alloy was found to be similar to that of metallic Cu. Reactive methanol adsorption was also investigated by in situ X-ray photoelectron spectroscopy for pressures between 3 x 10(-8) and 0.3 mbar.

IN-SITU CORE-LEVEL PHOTOELECTRON SPECTROSCOPY OF ADSORBATES ON SURFACES INVOLVING A MOLECULAR BEAM — GENERAL SETUP AND FIRST EXPERIMENTS

In this contribution we introduce a new apparatus combining high-resolution photoelectron spectroscopy and supersonic molecular beam techniques designed to follow simple surface reactions like adsorption, desorption or oxidation in situ in a time- and temperature-resolved manner. Using high brightness synchrotron radiation high resolution core-level spectra can be obtained in less than 3 s. The molecular beam allows for local pressures of up to 1 · 10-5 mbar and translational energies of the molecules of up to 2 eV in the case of CO. Preliminary examples of CO adsorption on Pt(111) are shown, where kinetic parameters can be derived from the coverage dependence of the different adsorption sites.

Properties of reactively sputtered Ag, Au, Pd, and Pt Schottky contacts on n-type ZnO

Highly rectifying Ag, Au, Pd, and Pt Schottky contacts have been fabricated on heteroepitaxial pulsed-laser deposited ZnO-thin films by reactive sputtering. X-ray photoelectron spectroscopy revealed an oxidation of the Ag, Pd, and Pt contact material; the gold contacts are purely metallic. The necessity of a conductive capping of the oxidized contacts is proven by photocurrent measurements of AgxO contacts. The ideality factors and the effective barrier heights were determined by current-voltage measurements. Capacitance-voltage and temperature dependent current-voltage measurements were furthermore carried out to determine the mean barrier height, the standard deviation and the respective voltage dependencies taking lateral fluctuations of the barrier height into account.

Activated adsorption of methane on Pt(1 1 1) —an in situ XPS study

We have investigated the activated adsorption of methane on Pt(1 1 1) by the combination of a supersonic molecular beam and in situ high-resolution X-ray photoelectron spectroscopy at the German synchrotron radiation facility BESSY II. On exposing the surface to a methane beam with kinetic energies between 0.30 and 0.83 eV, CH3 is formed as a stable species at 120 K; upon heating, at around 260 K the adsorbed methyl partly dehydrogenates to CH and partly recombines to methane, which desorbs. Upon adsorption at 300 K, CH is directly formed as a stable surface species. To verify the chemical identity of CH as an intermediate, we have also investigated the thermal evolution of a saturated ethylene layer. Upon heating, at ~290 K partial ethylene desorption and the formation of ethylidyne is clearly observed in the spectra, as expected from the literature. From the binding energies and also from the vibrational signature of the C 1s spectra, an unequivocal assignment of the various surface species is possible. Measurements of the sticking coefficients of methane show that the saturation coverage at 120 K depends on the kinetic energy of the molecule; furthermore, the sticking coefficient for vibrationally excited molecules is strongly enhanced.

Kinetics of the CO oxidation reaction on Pt(111) studied by in situ high-resolution x-ray photoelectron spectroscopy

High-resolution x-ray photoelectron spectroscopy has been used to study the kinetics of the CO oxidation reaction on a Pt(111) surface in situ. The study focuses on the interaction of a preadsorbed p(2x2) layer of atomic oxygen with CO dosed using a supersonic molecular beam. Measurements of O 1s and C 1s spectra at 120 K show that CO adsorbs on the oxygen precovered substrate, but no reaction occurs. A maximum CO coverage of 0.23 ML (monolayer) is observed, with CO exclusively bound on on-top sites. In accordance with the literature, bridge sites are blocked by the presence of atomic oxygen. The reaction of CO with preadsorbed O to CO(2) is studied isothermally in a temperature range between 275 and 305 K. The reaction rate initially increases with CO pressure, but saturates at 9x10(-7) mbar. The data indicate that a certain amount of disordered oxygen within the p(2x2) layer acts as a starting point of the reaction and for a given temperature reacts with a higher rate than O in the well-ordered oxygen p(2x2) phase. For the reaction of CO with this ordered phase, the results confirm the assumption of a reaction mechanism, which is restricted to the edges of compact oxygen islands. The activation energy of the reaction is determined to (0.53+/-0.04) eV, with a prefactor of 4.7x10(6+/-0.7) s(-1).

A site-selective in situ study of CO adsorption and desorption on Pt(355).

Using time-dependent high-resolution x-ray photoelectron spectroscopy at BESSY II, the adsorption and desorption processes of CO on stepped Pt(355) = Pt[5(111) x (111)] were investigated. From a quantitative analysis of C 1s data, the distribution of CO on the various adsorption sites can be determined continuously during adsorption and desorption. These unique data show that the terrace sites are only occupied when the step sites are almost saturated, even at temperatures as low as 130 K. The coverage-dependent occupation of on-top and bridge adsorption sites on the (111) terraces of Pt(355) is found to differ from that on Pt(111), which is attributed to the finite width of the terraces and changes in adsorbate-adsorbate interactions. In particular, no long-range order of the adsorbate layer could be observed by low-energy electron diffraction. Further details are derived from sticking coefficient measurements using the method devised by King and Wells [Proc. R. Soc. London, Ser. A 339, 245 (1974)] and temperature-programmed desorption. The CO saturation coverage is found to be slightly smaller on the stepped surface as compared to that on Pt(111). The initial sticking coefficient has the same high value of 0.91 for both surfaces.

A detailed analysis of vibrational excitations in x-ray photoelectron spectra of adsorbed small hydrocarbons.

The vibrational fine structure of x-ray photoelectron (XP) spectra of a number of different small hydrocarbon molecules and reaction intermediates adsorbed on Pt(111) and Ni(111) has been investigated in detail. The data for methyl, methylidyne, acetylene, and ethylene can consistently be analyzed within the linear coupling model. The S factor, i.e., the intensity ratio of the first vibrationally excited to the adiabatic transition, is obtained to be 0.17+/-0.02 per C-H bond; for the deuterated species a value of 0.23+/-0.02 is obtained. Therefore, the vibrational fine structure can be used for fingerprinting in the analysis of XP spectra and for identifying unknown reaction intermediates. From the data, Deltar, the change of the minimum in the potential energy curve upon core ionization, is calculated within the linear coupling model using a first order correction. For all adsorbates, including the deuterated ones, a value of Deltar=0.060+/-0.004 A is obtained. Furthermore, from the binding energy of the adiabatic peak and from the energy of the vibrational excitation in the ionic final state some information on the adsorbate/substrate bond and the adsorption site can be derived.

Sulfur Oxidation on Pt(355): It Is the Steps!

Platinum catalysts are frequently used in catalytic converters in cars and also in oil refineries. The catalysts’ active sites are subject to deactivation through poisoning by sulfur (or sulfur oxides), which are common impurities in fuels. These active sites are thought to be defects, such as step or kink sites, which are omnipresent on the surface of the highly dispersed catalyst nanoparticles. Adsorbed sulfur modifies the electronic properties of the catalyst surface, which leads to a decrease of chemical and catalytic activity. The key step to regain catalyst activity is the removal of the sulfur atoms from the catalyst surface, for example by exposing it to molecular oxygen, thereby oxidizing the adsorbed sulfur, and then removing the resulting SOx species from the surface. The mechanism, the chemical nature of the intermediates formed, and the specific role of defects in this process are unknown for the most part. This lack of insight is exists, because the relevant information can be obtained directly only by in situ methods, which allow a quantitative determination of the surface species or intermediates on the timescale of seconds. However, up to now there have been only very few studies for the direct measurement of kinetic parameters such as activation energies. In most cases kinetic parameters are determined by temperature-programmed desorption (TPD), where only the desorbing species are detected. Since important reaction intermediates can thereby easily be missed, the correct determination of kinetic parameters can be hampered. Herein we present the first in situ study of sulfur oxidation on a model catalyst surface, namely stepped Pt(355). We have clearly identified the steps as active sites and determined the activation energy directly. The Pt(355) surface has (111) terraces five atom rows wide, and monatomic steps with (111) orientation. The role of the steps is elucidated by comparison to data obtained on a flat Pt(111) surface. Using synchrotron radiation, we were able to measure high-resolution XP spectra in situ during adsorption and while heating the sample with short measuring times. Owing to the high resolution, different surface species could be identified and analyzed quantitatively and site selectively in a time-dependent fashion, also for very low adsorbate coverages. This enabled us to investigate the oxidation of small amounts of sulfur with oxygen present on the surface in large excess, which simplifies the kinetic analysis and makes it possible to determine the activation energy of the rate-determining step. The information on sulfur oxidation is rather limited in the literature. Early TPD studies on Pt(111) yielded no information on surface intermediates, and consequently only an apparent activation energy was derived. Theoretical calculations indicate that at the oxygen saturation limit S is oxidized to SOx (x = 1–4) and the total energy increases with x, but no information on the activation energy of the ratelimiting step is available. Furthermore, there are a number of studies on the adsorption of SO2 on Pt surfaces, which serve as reference for the identification of reaction intermediates and partial reaction steps in the present study. 11,21–23] The thermal evolution of a layer of coadsorbed sulfur and oxygen on Pt(355) provides a first overview of the relevant reaction steps. Figure 1a shows a series of S 2p spectra recorded before and after dosing of molecular oxygen at 250 K onto Pt(355) precovered with 0.020 monolayers (ML) of sulfur, and during subsequent heating of the coadsorbate layer. The spectrum in black (sulfur layer prior to exposure to oxygen) shows the S 2p3/2 and S 2p1/2 signals at 162.0 and 163.2 eV, respectively, with an intensity ratio of 2:1. As this ratio and the peak separation of these signals are identical for all sulfur species, only the stronger 2p3/2 signal will be discussed. The value of 162.0 eV is typical of S adsorbed at step sites on Pt(355). The spectrum in orange, which was recorded after saturation of the surface with oxygen, shows the S 2p3/2 peak at 162.2 eV, which is typical for S at terrace sites. The clearly discernable shift of 0.2 eV indicates that the S atoms were pushed away from the step to terrace sites by the O atoms, similar to a recent observation for the coadsorption of sulfur and carbon monoxide on Pt(355). When the sample is heated, the S 2p spectra in Figure 1a change dramatically. To visualize the thermal evolution more clearly, we have also plotted the data in a color-coded density plot in Figure 1b. For the quantitative analysis shown in Figure 1d, the spectra were fitted, with the energetic separation of the S 2p1/2 and 2p3/2 peaks fixed at 1.2 eVand their ratio set at 1:2 (see the Experimental Section). In Figure 1c a [*] R. Streber, Dr. C. Papp, M. P. A. Lorenz, Dr. A. Bayer, Prof. Dr. H.-P. Steinr ck Lehrstuhl f r Physikalische Chemie II Universit t Erlangen-N rnberg Egerlandstrasse 3, 91058 Erlangen (Germany) Fax: (+ 49)1931-852-8867 E-mail: steinrueck@chemie.uni-erlangen.de and Erlangen Catalysis Resource Center (ECRC) Universit t Erlangen-N rnberg Egerlandstrasse 3, 91058 Erlangen (Germany)