The surface structure of BaO on Pt(111): (2x2)-reconstructed BaO(111)

The surface structure of BaO(111) has been determined using STM and computer modelling. The BaO(111) surface was prepared in thin film form on Pt(111) and presents a surface with twice the lattice parameter expected for that of the bulk termination, i.e. a (2 x 2) reconstruction. Computer modelling indicates that the bulk termination is unstable, but that the (2 x 2) reconstructed BaO(111) surface has a low surface energy and is hence a stable surface reconstruction. The (2 x 2) reconstruction consists of small, three-sided pyramids with (100) oriented sides and either oxygen or barium ions at the apices. Less regular surface reconstructions containing the same pyramids are almost equally stable, indicating that we may also expect less regular regions to appear with a fairly random distribution of these surface species. The simulations further suggest that a regular (4 x 4) reconstruction built up of bigger pyramids is even more energetically favourable, and some evidence is found for such a structure in the STM. (c) 2006 Elsevier B.V. All rights reserved.

Surface chemistry of glycine on Pt{111} in different aqueous environments

Adsorption of glycine on Ptf111g under UHV conditions and in different aqueous environments was studied by XPS (UHV and ambient pressure) and NEXAFS. Under UHV conditions, glycine adsorbs in its neutral molecular state up to about 0.15 ML. Further deposition leads to the formation of an additional zwitterionic species, which is in direct contact with the substrate surface, followed by the growth of multilayers, which also consist of zwitterions. The neutral surface species is most stable and decomposes at 360 K through a multi-step process which includes the formation of methylamine and carbon monoxide. When glycine and water are co-adsorbed in UHV at low temperatures (< 170 K) inter-layer diffusion is inhibited and the surface composition depends on the adsorption sequence. Water adsorbed on top of a glycine layer does not lead to significant changes in its chemical state. When glycine is adsorbed on top of a pre-adsorbed chemisorbed water layer or thick ice layer, however, it is found in its zwitterionic state, even at low coverage. No difference is seen in the chemical state of glycine when the layers are exposed to ambient water vapor pressure up to 0.2 Torr at temperatures above 300 K. Also the decomposition temperature stays the same, 360 K, irrespective of the water vapor pressure. Only the reaction path of the decomposition products is affected by ambient water vapor.

Surface termination of CePt5/Pt(111): the key to chemical inertness

The surface termination of CePt5/Pt(111) is determined experimentally by LEED-IV. In accordance with recent theoretical predictions, a dense Pt terminated surface is being found. Whereas the CePt5 volume lattice comprises Pt kagome layers, additional Pt atoms occupy the associated hole positions at the surface. This finding provides a natural explanation for the remarkable inertness of the CePt5 intermetallic. Implications of the structural relaxations determined by LEED-IV analysis are discussed with regard to observations by scanning tunneling microscopy and electron spectroscopies.

Theory of enhanced magnetic anisotropy induced by Pt adatoms on two-dimensional Co clusters supported on a Pt(111) substrate

Calculations are reported of the magnetic anisotropy energy of two-dimensional (2D) Co nanostructures on a Pt(111) substrate. The perpendicular magnetic anisotropy (PMA) of the 2D Co clusters strongly depends on their size and shape, and rapidly decreases with increasing cluster size. The PMA calculated is in reasonable agreement with experimental results. The sensitivity of the results to the Co-Pt spacing at the interface is also investigated and, in particular, for a complete Co monolayer we note that the value of the spacing at the interface determines whether PMA or in-plane anisotropy occurs. We find that the PMA can be greatly enhanced by the addition of Pt adatoms to the top surface of the 2D Co clusters. A single Pt atom can induce in excess of 5 meV to the anisotropy energy of a cluster. In the absence of the Pt adatoms the PMA of the Co clusters falls below 1 meV/Co atom for clusters of about 10 atoms whereas, with Pt atoms added to the surface of the clusters, a PMA of 1 meV/Co atom can be maintained for clusters as large as about 40 atoms. The effect of placing Os atoms on the top of the Co clusters is also considered. The addition of 5d atoms and clusters on the top of ferromagnetic nanoparticles may provide an approach to tune the magnetic anisotropy and moment separately.

The structure of the mixed OH+H2O overlayer on Pt{111}

The structure of the mixed p(3x3)-(3OH+3H(2)O) phase on Pt{111} has been investigated by low-energy electron diffraction-IV structure analysis. The OH+H2O overlayer consists of hexagonal rings of coplanar oxygen atoms interlinked by hydrogen bonds. Lateral shifts of the O atoms away from atop sites result in different O-O separations and hexagons with only large separations (2.81 and 3.02 angstrom) linked by hexagons with alternating separations of 2.49 and 2.81/3.02 A. This unusual pattern is consistent with a hydrogen-bonded network in which water is adsorbed in cyclic rings separated by OH in a p(3x3) structure. The topmost two layers of the Pt atoms relax inwards with respect to the clean surface and both show vertical buckling of up to 0.06 angstrom. In addition, significant shifts away from the lateral bulk positions have been found for the second layer of Pt atoms. (C) 2005 American Institute of Physics.

Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

A stable pure hydroxyl layer on Pt{110}-(1x2)

The adsorption of water and coadsorption with oxygen on the missing-row reconstructed Pt{110}-(1x2) surface was studied by using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Coadsorbed oxygen below saturation (<0.65 +/- 0.05 ML) leads to the formation of 014, which occupies sites near the ridge Pt atoms, In contrast to the more closely packed Pt{111} Surface, OH appears not to form hydrogen bonds with coadsorbed water molecules and is stable after the desorption of water tip to about 205 K (as determined by TPD). Because OH and atomic oxygen compete for adsorption sites, water dissociation is only observed for oxygen coverages below saturation. In the absence of coadsorbed oxygen, water stays intact at all temperatures and forms a strongly bound layer of 2 ML coverage oil the clean Pt{110}-(1x2) surface at temperatures between 140 and 175 K.

The Structure of the chiral Pt{531} surface: a combined LEED and DFT study

The structure of the chiral kinked Pt{531} surface has been determined by low-energy electron diffraction intensity-versus-energy (LEED-IV) analysis and density functional theory (DFT). Large contractions and expansions of the vertical interlayer distances with respect to the bulk-terminated surface geometry were found for the first six layers (LEED: d(12) = 0.44 angstrom, d(23) = 0.69 angstrom, d(34) = 0.49 angstrom, d(45) = 0.95 angstrom, d(56) = 0.56 angstrom; DFT: d(12) = 0.51 angstrom, d(23) = 0.55 angstrom, d(34) = 0.74 angstrom, d(45) = 0.78 angstrom, d(56) = 0.63 angstrom; d(bulk) = 0.66 angstrom). Energy-dependent cancellations of LEED spots over unusually large energy ranges, up to 100 eV, can be explained by surface roughness and reproduced by applying a model involving 0.25 ML of vacancies and adatoms in the scattering calculations. The agreement between the results from LEED and DFT is not as good as in other cases, which could be due to this roughness of the real surface.

Effect of oxygen adsorption on the chiral pt{531} surface

The adsorption of oxygen on the chiral Pt{531} surface was studied by high-resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). After the surface is annealed in oxygen (3 x 10(-7) mbar), three O 1s peaks are observed in XPS. One peak, at 529.5 eV, is assigned to chemisorbed oxygen; it disappears after annealing in vacuo to temperatures above 900 K. The other two peaks at 530.8 and 532.3 eV are stable up to at least 1250 K. They are associated with oxide clusters on the surface. These clusters readily react with coadsorbed carbon monoxide at temperatures between 315 and 620 K.

Redox behavior of the model catalyst Pd/CeO2-x/Pt(111)

Photoelectron spectroscopy and scanning tunneling microscopy have been used to investigate how the oxidation state of Ce in CeO2-x(111) ultrathin films is influenced by the presence of Pd nanoparticles. Pd induces an increase in the concentration of Ce3+ cations, which is interpreted as charge transfer from Pd to CeO2-x(111) on the basis of DFT+U calculations. Charge transfer from Pd to Ce4+ is found to be energetically favorable even for individual Pd adatoms. These results have implications for our understanding of the redox behavior of ceria-based model catalyst systems.

Preventing carbon contamination of optical devices for X-rays: the effect of oxygen on photon-induced dissociation of CO on platinum

Platinum is one of the most common coatings used to optimize mirror reflectivity in soft X-ray beamlines. Normal operation results in optics contamination by carbon-based molecules present in the residual vacuum of the beamlines. The reflectivity reduction induced by a carbon layer at the mirror surface is a major problem in synchrotron radiation sources. A time-dependent photoelectron spectroscopy study of the chemical reactions which take place at the Pt(111) surface under operating conditions is presented. It is shown that the carbon contamination layer growth can be stopped and reversed by low partial pressures of oxygen for optics operated in intense photon beams at liquidnitrogen temperature. For mirrors operated at room temperature the carbon contamination observed for equivalent partial pressures of CO is reduced and the effects of oxygen are observed on a long time scale.

The surface geometry of carbonmonoxide and hydrogen co-adsorbed on Ni 111

A combination of photoelectron spectroscopy, temperature programmed desorption and low energy electron diffraction structure determinations have been applied to study the p(2 x 2) structures of pure hydrogen and co-adsorbed hydrogen and CO on Ni {111}. In agreement with earlier work atomic hydrogen is found to adsorb on fcc and hcp sites in the pure layer with H-Ni bond lengths of 1.74Angstrom. The substrate interlayer distances, d(12) = 2.05Angstrom and d(23) = 2.06Angstrom, are expanded with respect to clean Ni {111} with buckling of 0.04Angstrom in the first layer. In the co-adsorbed phase Co occupies hcp sites and only the hydrogen atoms on fcc sites remain on the surface. d(12) is even further expanded to 2.08Angstrom with buckling in the first and second layer of 0.06 and 0.02Angstrom, respectively. The C-O, C-Ni, and H-Ni bond lengths are within the range of values also found for the pure adsorbates.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Chemical composition and reactivity of water on clean and oxygen-covered Pd{111}

The chemical composition and dissociation behaviour of water adsorbed on clean and oxygen pre-covered Pd{111} was studied using high-resolution time-resolved and temperature-programmed X-ray photoelectron spectroscopy. We find that water remains intact at all temperatures up to desorption on the clean surface and at high oxygen coverage(0.69 ML) when a surface oxide is formed. The highest desorption peaks occur at 163 K from the clean surface and at 172 K from the surface oxide. At the intermediate coverage of 0.20 ML oxygen reacts with coadsorbed water at 155 K, to generate a mixed H2O/OH layer exhibiting a (root 3- x root 3)R30 degrees diffraction pattern, which is stable up to 177 K. The measured ratio between intact water and the hydroxyl species in this layer varies between 1.5 and 2 depending on temperature. (C) 2008 Elsevier B.V. All rights reserved.

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (<0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (>0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.