Kevin C. Prince

Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles

Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.

Oxygen adsorption on silver (110): Dispersion, bonding and precursor state

Abstract Angle-resolved photoemission, both in the laboratory and with synchrotron radiation, has been used to investigate three states of adsorbed oxygen on Ag(110): chemisorbed atomic oxygen, undissociated chemisorbed dioxygen and physisorbed molecular oxygen. For atomic oxygen, dispersion of adsorbate-induced levels was observed indicating strong oxygen-oxygen interaction in the [001] direction. Polarised light combined with selection rules was used to determine the symmetry of the adsorbate-derived bands. The adsorption geometry and symmetry of the oxygen-induced levels for the chemisorbed dioxygen species were also investigated with the selection rules. The molecule appears to lie parallel to the surface with the OO axis oriented in the [110] direction. The adsorbate-induced feature of lowest ionisation potential at 1.1 eV relative to E F is 1 π g -derived. The very low frequency reported for the OO stretch and the analogy with coordination chemistry also suggest that the chemisorbed dioxygen species is lying down on the surface. At sufficiently low temperature, oxygen was found to physisorb on the bare metal also with its OO axis parallel to the surface. We identify physisorbed oxygen as an intrinsic precursor state for chemisorption.

SPELEEM: Combining LEEM and Spectroscopic Imaging

At present the only surface electron microscope which allows true characteristic XPEEM (photoemission electron microscopy using synchrotron radiation) and structural characterization is the spectroscopic LEEM developed at the Technical University Clausthal in the early nineties. This instrument has in the past been used mainly for LEEM studies of various surface and thin film phenomena, because it had very limited access to synchrotron radiation. Now the microscope is connected quasipermanently to the undulator beamline 6.2 at the storage ring ELETTRA, operating successfully since the end of 1996 under the name SPELEEM (Spectroscopic PhotoEmission and Low Energy Electron Microscope). The high brightness of the ELETTRA light source, together with an optimized instrument, results in a spatial resolution better than 25 nm and an energy resolution better than 0.5 eV in the XPEEM mode. The instrument can be used alternately for XPEEM, LEEM, LEED (low energy electron diffraction), MEM (mirror electron microscopy) and other imaging modes, depending upon the particular problem studied. The combination of these imaging modes allows a comprehensive characterization of the specimen. This is of particular importance when the chemical identification of structurar features is necessary for the understanding of a surface or thin film process. In addition, PED (photoelectron diffraction) and VPEAD (valence photoelectron angular distribution) of small selected areas give local atomic configuration and band structure information, respectively.

The high resolution Gas Phase Photoemission beamline, Elettra

Abstract The Gas Phase Photoemission beamline at Elettra has been commissioned with outstanding success. All photoabsorption spectra taken between 90 and 900 eV have shown resolution which is equal to or higher than any published spectra. The monochromator is a variable angle spherical grating instrument (plane mirror and grating between entrance and exit slits), with an undulator as the source. Some of the problems encountered in commissioning and their solutions are discussed. In particular the calibration is complicated by the fact that an infinite number of angle pairs of the mirror and grating exist for a particular photon energy, whereas only one angle pair gives the highest resolution. A second problem is that the resolution is so high that above about 80 eV, it is much smaller than the lifetime broadening of any known absorption resonance, making any determination of resolution difficult. The experimental chambers available for users are described together with some examples of spectra which have been taken.

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser

Theory predicts that double-core-hole (DCH) spectroscopy can provide a new powerful means of differentiating between similar chemical systems with a sensitivity not hitherto possible. Although DCH ionization on a single site in molecules was recently measured with double- and single-photon absorption, double-core holes with single vacancies on two different sites, allowing unambiguous chemical analysis, have remained elusive. Here we report that direct observation of double-core holes with single vacancies on two different sites produced via sequential two-photon absorption, using short, intense X-ray pulses from the Linac Coherent Light Source free-electron laser and compare it with theoretical modeling. The observation of DCH states, which exhibit a unique signature, and agreement with theory proves the feasibility of the method. Our findings exploit the ultrashort pulse duration of the free-electron laser to eject two core electrons on a time scale comparable to that of Auger decay and demonstrate possible future X-ray control of physical inner-shell processes.

Tautomerism in cytosine and uracil: an experimental and theoretical core level spectroscopic study

The O, N, and C 1s core level photoemission spectra of the nucleobases cytosine and uracil have been measured in the vapor phase, and the results have been interpreted via theoretical calculations. Our calculations accurately predict the relative binding energies of the core level features observed in the experimental photoemission results and provide a full assignment. In agreement with previous work, a single tautomer of uracil is populated at 405 K, giving rise to relatively simple spectra. At 450 K, three tautomers of cytosine, one of which may consist of two rotamers, are identified, and their populations are determined. This resolves inconsistencies between recent laser studies of this molecule in which the rare imino-oxo tautomer was not observed and older microwave spectra in which it was reported.

Wetting of Si surfaces by Au–Si liquid alloys

The behavior of liquid Au–Si alloys on Si surfaces covered by a monolayer of gold has been investigated by ultrahigh-vacuum scanning electron microscopy. On the (111) surface, the alloy displays a constant contact angle with the surface from the eutectic temperature up to a temperature of 650 °C and thereafter the contact angle increases linearly with temperature. As observed in previous work, the shape of the liquid droplets changes from circular at lower temperature to hexagonal at higher temperature. In contrast, on the (100) surface, the contact angle increases linearly from the eutectic temperature to high temperature. The behavior of the shape of the droplets is, however, reversed: it is polygonal (octagonal) at lower temperature and becomes round at higher temperature. This behavior is explained in terms of the relative surface energy of the two surfaces and changing line tension of the liquid–solid–vapor phase line. In addition, the behavior of Au–Si droplets on vicinal and patterned surfaces of S...

An X-ray absorption and photoelectron diffraction study of the Cu{100} c(2 × 2) CO structure

Abstract The structure of CO adsorbed on Cu{100} has been investigated using near edge X-ray absorption fine structure at the oxygen K-edge to determine the molecular orientation, and normal emission photoelectron energy-intensity spectra for the C 1s and O 1s core levels to determine the adsorption site. The photoelectron diffraction data have been interpreted by comparison with the results of single scattering model calculations. Good agreement is found for CO molecules adsorbed normal to the surface on on-top sites with a CuC distance of 1.92±0.05 A , in accordance with a previous LEED study. Calculations show that intramolecular scattering can be rather unimportant for this technique and that the individual atomic sites may then be obtained from the photoelectron diffraction spectrum by studying the emission from the relevant atom and scattering from the substrate. The method should therefore be applicable to more complex molecular adsorbates.

Electronic structure of aromatic amino acids studied by soft x-ray spectroscopy

The electronic structure of phenylalanine, tyrosine, tryptophan, and 3-methylindole in the gas phase was investigated by x-ray photoemission spectroscopy (XPS) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the C, N, and O K-edges. The XPS spectra have been calculated for the four principal conformers of each amino acid, and the spectra weighted by the Boltzmann population ratios calculated from published free energies. Instead of the single peaks expected from the stoichiometry of the compounds, the N 1s core level spectra of phenylalanine and tryptophan show features indicating that more than one conformer is present. The calculations reproduce the experimental features. The C and O 1s spectra do not show evident effects due to conformational isomerism. The calculations predict that such effects are small for carbon, and for oxygen it appears that only broadening occurs. The carbon K-edge NEXAFS spectra of these aromatic amino acids are similar to the published data of the corresponding molecules in the solid state, but show more structure due to the higher resolution in the present study. The N K-edge spectra of tryptophan and 3-methylindole differ from phenylalanine and tyrosine, as the first two both contain a nitrogen atom located in a pyrrole ring. The nitrogen K-edge NEXAFS spectra of aromatic amino acids do not show any measurable effects due to conformational isomerism, in contrast to the photoemission results. Calculations support this result and show that variations of the vertical excitation energies of different conformers are small, and cannot be resolved in the present experiment. The O NEXAFS spectra of these three aromatic compounds are very similar to other, simpler amino acids, which have been studied previously.

Core Level Study of Alanine and Threonine

Core level X-ray photoemission spectra (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectra of alanine and threonine in the gas phase have been measured at the carbon, nitrogen, and oxygen K edges and interpreted in the light of theoretical calculations. For the computations, a set of approximations is made which allows sufficiently accurate calculations of several conformers to be performed in reasonable computing time. The accuracy has been checked by comparing results obtained for proline to our previous, higher level calculations. The photoemission spectra at the carbon and oxygen edges are assigned and compared. The nitrogen 1s photoemission peaks show anomalous broadening which we relate to the populations and types of conformers. The carbon K-edge NEXAFS spectra of alanine and threonine are compared with our previous data on glycine and resonances assigned accordingly. The nitrogen K-edge NEXAFS spectra of alanine and threonine do not show measurable effects due to the population of conformers, in contrast to the photoemission results. At the oxygen K edge, the spectra of these amino acids are similar with two prominent peaks assigned to transitions of O 1s electrons from the oxo and hydroxyl groups to vacant pi* and sigma* orbitals and additional intensity for threonine due to the second OH group. Conformer effects are observable in photoemission but appear to be more difficult to resolve in photoabsorption. We explain this by energetic shifts of opposite sign for the core hole states and unoccupied orbitals, which causes partial cancelation in NEXAFS but not in photoemission.