Interplay between ordered growth and intermixing of Pt on patterned Au surfaces

We have investigated the growth of submonolayer coverage of platinum on two gold surfaces (Au(1 1 1) and Au(7 8 8)), at temperatures ranging from 110 K to 300 K. The Scanning Tunneling Microscope images reveal a competition between the ordered growth of nanodots and a random intermixing between Pt and Au. The Pt deposition on the Au(1 1 1) surface at room temperature shows an ordered growth limited by the insertion of Pt atoms into the surface layer and the subsequent modifications of the herringbone surface pattern. In contrast, for Pt on the Au(7 8 8) stepped surface, perfect ordered growth is observed over a wide temperature range.     

Growth and characterization of Au,Ni and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh

The nucleation and thermal stability of Au, Ni, and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh as well as the interaction between Au–Ni bimetallic clusters and reactive gases have been studied by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Both Au and Ni atoms grow as three-dimensional (3D) clusters. Annealing the Au/carbon nanomesh surface up to 1150 °C leads to complete desorption of the Au clusters, while interfacial reaction occurs between Ni clusters and the substrate surface when the Ni clusters are subjected to the same annealing process. The nucleation of Au–Ni clusters depends critically on the deposition sequence. Au atoms preferentially nucleate on the existing Ni clusters, leading to the formation of bimetallic clusters with Au enriched on the surface. If the deposition sequence is reversed, a part of Ni atoms nucleate between the Au clusters. The thermal stability of the Au–Ni clusters resembles that of the Ni/carbon nanomesh surface, irrespective of the deposition sequence. XPS characterization reveals that Ni atoms in Au–Ni bimetallic clusters are oxidized upon exposure to 5.0 × 10^? 7 mbar O₂ for 5 min at room temperature while negligible structure change can be detected when the bimetallic clusters are exposed to CO gas under the similar conditions.     

The adsorption of acetic acid on clean and oxygen-covered Au/Pd(100) alloy surfaces

The adsorption of acetic acid is studied on clean and oxygen-covered Au/Pd(100) alloys as a function of gold content by temperature-programmed desorption and reflection–absorption infrared spectroscopy. Au/Pd(100) forms ordered alloys such that, for gold coverages above ~ 0.5 monolayers, only isolated palladium atoms surrounded by gold nearest neighbors are present. Predominantly molecular acetic acid forms on Au/Pd(100) alloy surfaces for gold coverages greater than ~ 0.56 ML, and desorbs with an activation energy of ~ 59 kJ/mol. Heating this surface also forms some η¹-acetate species which decompose to form CO and hydrogen. On alloy surfaces with palladium–palladium bridge sites, η¹-acetate species initially form, but rapidly convert into η²-species. They thermally decompose to form CO and hydrogen, with a small portion rehydrogenating to form acetic acid between 280 and 321 K depending on gold coverage. The presence of oxygen on both Pd(100) and Au/Pd(100) alloys facilitates acetate dehydrogenation so that only η²-acetate species form on these surfaces. The presence of oxygen also serves to stabilize the acetate species.     

Binding of single gold atoms on thin MgO(001) films

In the present Letter the first electron paramagnetic resonance spectra of single metal atoms on a single crystalline oxide surface are presented. For Au atoms on a MgO(001) film investigated here an analysis of the angular dependent resonance positions and the hyperfine coupling to (17)O shows that the atoms are bound on top of oxygen ions on the terrace of the film. This result is in perfect agreement with scanning tunneling microscopy measurements at 5 K presented here. The measured hyperfine matrix components allow an experimental verification of the theoretically proposed binding mechanism of Au atoms on MgO. In particular, the large reduction of the isotropic hyperfine coupling constant of supported Au as compared to free atoms is not due to a charge transfer at the interface but a hybridization of orbitals and a resulting polarization of the unpaired electron.     

Atomic structure of two-dimensional binary surface alloys: Si(111)-√21 × √21 superstructure

The atomic structures of Au and Ag co-adsorption-induced √21 × √21 superstructure on a Si(111) surface, i.e., (Si(111)-√21 × √21-(Au, Ag)), where the Si(111)-5 × 2-Au surface is used as a substrate, have been investigated using reflection high-energy positron diffraction (RHEPD) and photoemission spectroscopy. From core-level spectra, we determined the chemical environments of Ag and Au atoms present in the Si(111)-√21 × √21-(Au, Ag) surface. From the rocking curve and pattern analyses of RHEPD, we found that the atomic coordinates of the Au and Ag atoms were approximately the same as those of the Au and Ag atoms in other Si(111)-√21 × √21 surfaces with different stoichiometries. On the basis of the core-level and RHEPD results, we revealed the atomic structure of the Si(111)-√21 × √21-(Au, Ag) surface.     

Vibration spectroscopy of water on stepped gold surfaces

The vibration spectrum of H₂O (ice) adsorbed at low temperatures on Au(1 0 0), Au(1 11 1), and Au(1 1 5) is studied using electron energy loss spectroscopy. On the Au(1 0 0) surface, the spectra show the presence of the typical H-bonded network of water molecules for all coverages from the submonolayer into the multilayer range. The absence of a non-H-bonded OH-stretching mode is indicative for the “H-down bilayer”. On stepped surfaces, on the other hand, a considerable fraction of the H-atoms remains in the non-H-bonded state; surprisingly even in the multilayer range, and even after annealing. The fraction of non-H-bonded hydrogen atoms scales with the step density. Spectral features of water adsorbed at step-sites are isolated after annealing a surface exposed to small doses of H₂O. The results are discussed in the context of recent theoretical studies as well as in conceivable relation to the experimentally found reduction of the Helmholtz-capacitance on stepped Au(1 1 n) electrodes.     

Chemical properties of structurally well-defined PdRu/Ru(0 0 0 1) surface alloys – Interaction with CO

The chemical properties of structurally well-defined PdRu/Ru(0 0 0 1) monolayer surface alloys [H. Hartmann, T. Diemant, A. Bergbeiter, J. Bansmann, H.E. Hoster, R.J. Behm, Surf. Sci. in press, doi:10.1016/j.sucs.2008.10.055.] and a Pd monolayer on Ru(0 0 0 1) were studied by temperature programmed desorption and infrared reflection absorption spectroscopy using CO as probe molecule. IR experiments on the PdRu/Ru(0 0 0 1) surface alloys demonstrate that CO adsorption on Ru sites resembles that on pure Ru(0 0 0 1) (on-top adsorption), while adsorption on the Pd sites occurs on both multifold coordinated and on-top sites, similar to CO on Pd(1 1 1). A significant destabilization of CO adsorption on Pd sites for both, surface alloys and the Pd monolayer film, compared to pure Pd(1 1 1) surfaces is attributed to a combination of geometric strain and vertical electronic ligand effects; an additional variation in the CO adsorption bond strength in the surface alloys is attributed to changes in the neighboring surface atom shell (lateral ligand effects). The chemical modifications introduced by PdRu surface alloy formation are compared with findings for deuterium adsorption on the same surface alloys; effects of the two-dimensional (2D) distribution of surface atoms are illustrated by comparison with CO adsorption on PtRu/Ru(0 0 0 1) surface alloys, where in contrast to the pronounced 2D phase segregation in PdRu/Ru(0 0 0 1) the surface atoms are essentially randomly distributed.     

Experimental measurements of the energetics of surface reactions

Microcalorimetric measurements of the adsorption energies of well-defined surface species are reviewed, using selected examples mainly from our own group to demonstrate the types of information that can be achieved with this technique. The adsorption energies of molecules on single crystal transition metal surfaces to produce well-characterized molecular or dissociated adsorbates allow determination of the standard enthalpies of formation of key catalytic reaction intermediates. The adsorption energies for metal atoms during metal thin-film growth allow quantitative estimates of metal-substrate bond energies, metal film/substrate adhesion energies and the energetic costs associated with lattice mismatch during thin film growth. Results for several metals on MgO(1 0 0) reveal that they bind weakly to terrace sites. Metals from the right side of the periodic table also bind weakly to step and kink sites (although more strongly than on terraces), whereas alkali and alkaline earth metals bind very strongly to these defects. At 300 K, metals tend to form 2D or 3D clusters nucleated on MgO(1 0 0) defects, via a transiently adsorbed precursor (mobile adatoms on terraces). Calorimetric measurement of the energy of metal atoms in supported 3D metal nanoparticles as a function of particle size reveals a very strong size dependence below 6 nm diameter. Metal atoms also adsorb weakly on polymer surfaces and nucleate 3D metal particles, sometimes in kinetic competition with migration to and strong reaction with the more reactive, subsurface organic functional groups. Measurements of the energies for adsorbed proteins on calcium phosphate crystals, which have been structurally characterized by NMR, reveal extremely weak binding dominated by the entropy gained from release of organized water. These experimental measurements of the energies of well-defined adsorbates serve as benchmarks against which to compare theoretical computations for accuracy, thus enabling improvement upon quantum mechanical methods. Comparisons of calorimetric adsorption energies on single crystal surfaces with state-of-the-art DFT calculations show that the latter can often be in substantial (?20%) error.     

CO and H2O adsorption and reaction on Au(310)

We have studied desorption of ¹³CO and H₂O and desorption and reaction of coadsorbed, ¹³CO and H₂O on Au(310). From the clean surface, CO desorbs mainly in, two peaks centered near 140 and 200 K. A complete analysis of desorption spectra, yields average binding energies of 21 ± 2 and 37 ± 4 kJ/mol, respectively. Additional desorption states are observed near 95 K and 110 K. Post-adsorption of H₂O displaces part of CO pre-adsorbed at step sites, but does not lead to CO oxidation or significant shifts in binding energies. However, in combination with electron irradiation, ¹³CO₂ is formed during H₂O desorption. Results suggest that electron-induced decomposition products of H₂O are sheltered by hydration from direct reaction with CO.     

Infrared study of triruthenium dodecacarbonyl interactions with gold

We present here a study of the interaction of triruthenium dodecacarbonyl Ru₃(CO)₁₂ with gold surfaces using time-evolved and temperature-programmed infrared reflection absorption spectroscopy (IRAS) and STM. Ru₃(CO)₁₂ exhibits drastically different adsorption/desorption behavior on high-index surfaces of gold in comparison to the smooth Au(111) surface. On the smooth Au(111) surface, the adsorption of Ru₃(CO)₁₂ at 200 K is observed to be molecular and reversible with the molecule's Ru₃-plane oriented essentially perpendicular to the surface in the first and second layer. In the multilayer (> 3 ML), the molecule is oriented parallel (or moderately inclined) to the surface. On high-index gold surfaces, prepared by partial annealing of rough gold films, the molecules dissociate. Vibrational spectra reveal dissociation of carbonyl to Ru and CO at elevated temperature (> 250 K) with the formation of CO covered Ru-islands and the subsequent desorption of CO from Ru-islands. Increasing amounts of CO observed with increasing surface roughness demonstrate that the rate of Ru₃(CO)₁₂ dissociation is related directly to the surface roughness of the gold surface. STM images reveal at low coverage the formation of 2-D islands of carbonyl fragments with lateral sizes of 1 to 1.5 nm and at higher coverage the formation of larger 3-D islands of 1 to 3 layers and lateral sizes above 10 nm.     

Theoretical understanding of adlayer structure,thermal stability and electronic property of graphene molecules

The geometry of hexafluorotribenzo[a,g,m]coronene with n-carbon alkyl chains [FTBC-Cn (n = 4, 6, 8, 12)] and their supramolecule self-assembly on a highly oriented pyrolytic graphite (HOPG) surface has been optimized by molecular dynamics simulations using COMPASS force field at 0 K, 298 K, 333 K and 353 K. Electronic properties and intermolecular interactions in graphene supramolecule assembly have been studied by the first principle methods based on the density functional theory (DFT). It is indicated that the thermal stability and electronic properties of graphene molecules can be tunable by attaching alkyl chains to a triangular graphene sheet, and changing the length of the alkyl chain, and self-assembling on a certain substrate. The main results are as follows. The geometry and energy gap of the FTBC-Cn single molecule and their supramolecule self-assembly on HOPG are both stable with the changes of the temperature from 0 K to 353 K and the number of carbon atoms on the alkyl chain. The simulation results of geometry, energy gap as well as STM images of graphene supramolecule assembly are in good agreement with the corresponding experimental results in room temperature. Furthermore, the electronic properties of graphene supramolecule assembly at the temperatures of 0 K, 333 K and 353 K are also predicted. When a triangular graphene molecule attached with six alkyl chains, the energy gaps are increased and stabilized at the temperature from 0 K to 353 K. After FTBC-Cn molecule self-assembly on a HOPG substrate, the energy gap is reduced but still stable.     

PtCo/Au nanocomposite: Synthesis,characterization, and magnetic properties

Magnetic PtCo/Au nanocomposites with narrow size distribution were synthesized in a reverse micelle, followed by a post-synthesis handling of the stabilizer-exchange technique. The PtCo/Au nanocomposites were characterized by ultraviolet visible spectroscopy, X-ray diffraction and transmission electron microscopy, respectively. Superconducting quantum interference device studies revealed that the nanocomposites were superparamagnetic above the blocking temperature (T_B=69 K), while the samples were ferromagnetic with Hc (628 Oe) and Ms (2.97 emu/g) at 5 K.     

Exploring the role of samarium in the modification of rhodium catalysts through surface science approach

In this paper we review the preparation and reaction properties of ordered SmRh surface alloys and SmO_x/Rh(1 0 0) model catalyst which have been systematically investigated by low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and temperature desorption spectroscopy (TDS). The growth of Sm on Rh(1 0 0) at room temperature follows the Stranski-Krastanov mode. Thermal treatment of the Sm films on Rh(1 0 0) leads to the formation of ordered SmRh surface alloys. An “inverse” SmO_x/Rh(1 0 0) model catalyst is produced under controlled oxidation of the SmRh surface alloy. CO adsorption on the SmRh alloy and SmO_x/Rh(1 0 0) surfaces gives rise to five TDS characteristic features originating from different adsorption sites. Both the site blocking of SmO_x and the electron transfer between SmO_x and Rh substrate significantly affect the CO adsorption. Acetate decomposition on both Rh(1 0 0) and the SmO_x/Rh(1 0 0) surfaces are found to undergo two competitive pathways that yields either (i) CO(a) and O(a) or (ii) CO₂(g) and H₂(g) at high temperature. The reactive desorption of acetic acid on SmO_x/Rh(1 0 0) is dramatically different from that on Rh(1 0 0). A rapid decomposition of acetic acid to produce CO(g) and CO₂(g) can be observed only on SmO_x/Rh(1 0 0), where CO(g) becomes the predominant product at 225 K, indicating a strong promotional effect of SmO_x in the selective decomposition of acetate. Finally, we briefly describe the future outlook of research on rare earth oxide/metal model catalysts.     

Growth mode of Pt1−xNix films biased dc-sputter-deposited on MgO(0 0 1)

A study is made by TEM, XRD and by measuring electrical/magnetic properties, of growth mode and properties of Pt_1−xNi_x alloy films deposited on MgO(0 0 1) at 250°C by dc-sputtering at 2.5–2.7 kV in Ar. A bias voltage V_s≤−160 V was applied to the substrate during deposition. It was confirmed that the Pt film was polycrystalline with the texture of Pt(1 1 1)/MgO(0 0 1) while the films of Pt_0.14Ni_0.86 and Pt_0.19Ni_0.81 were epitaxially grown with Pt–Ni(0 0 1)[1 0 0]/MgO(0 0 1)[1 0 0] similarly to the case of Ni/MgO(0 0 1). Thus the growth mode transformation between Pt–Ni(1 1 1)/MgO(0 0 1) and Pt–Ni(0 0 1)/MgO(0 0 1) may be induced at x less than 0.81 for Pt_1−xNi_x alloy films. The temperature coefficient of resistance TCR from 100 to 300 K of Pt_0.14Ni_0.86 films was estimated to be 0.0044–0.0053 K⁻¹ and saturation magnetization at 300 K to be 1.7–3.2 kG, respectively, while TCR of Pt films was estimated to be 0.0035–0.0048 K⁻¹.     

Reactivity of the Cu2O(1 0 0) surface: Insights from first principles calculations

We present a summary of results of systematic first principles calculations of the electronic and geometric structures of the Cu₂O(1 0 0) surface and the process of CO oxidation on this surface (energetics and pathways of adsorption, diffusion and reactions of CO and O₂ on the surface). The (p, T) phase diagram of the Cu₂O(1 0 0) in equilibrium of with gas phase O₂ built using the ab initio thermodynamics approach suggests that the O-terminated surface is preferred over the Cu-terminated one within the entire ranges of pressures and temperatures in which the compound exists. Metastable Cu-terminated Cu₂O(1 0 0) is found to undergo a surface reconstruction in agreement with experiment. We find CO to oxidize spontaneously on the O-terminated Cu₂O(1 0 0) surface by consuming surface O atoms. Our calculations also show that the surface O-vacancies left in the course of the CO oxidation can be easily filled with dissociative adsorption of the gas phase O₂ molecules, which are usually present in reaction environment.     

Does methanol produce a stable methoxy species on Ru(0001) at low temperatures?

Soft X-ray photoelectron spectroscopy (SXPS) and energy-scanned photoelectron diffraction (PhD) have been used to study the surface species produced by exposure of Ru(0001) to methanol at ~ 150 K. SXPS shows a single surface species is formed at sub-monolayer coverages with an O 1s peak binding energy of ~ 532.6 eV, 2.8 eV greater than that of chemisorbed atomic oxygen. O 1s PhD data from this species shows no significant modulations, in contrast to simulated PhD spectra from a methoxy species occupying a three-fold coordinated hollow site, as predicted by earlier density functional theory calculations, or atop or bridging sites. By contrast, PhD data from the O 1s of the atomic oxygen species in the Ru(0001)(2 × 1)–O phase are consistent with the oxygen atoms occupying ‘hcp’ hollow sites (above second-layer Ru atoms) at a RuO bondlength of 2.01 ± 0.02 Å, essentially identical to previous structure determinations of this phase. O 1s PhD recorded at normal emission from adsorbed CO are also consistent with the known CO atop adsorption species. We conclude that the methanol-derived surface molecular species is not methoxy in a well-defined local site on the surface, but is consistent with clusters of intact methanol identified in a recent infrared spectroscopy investigation.     

Magnetic properties and structures of Fe/MgF2 multilayered films

Multilayers composed of Fe and MgF₂ with layer thicknesses between 9 Å and 100 Å and of 30 Å, respectively, were prepared with an ultrahigh-vacuum deposition technique. Medium-angle X-ray data show that the Fe layers in the BCC phase have considerable (1 1 0) texture. Periodicity due to multilayered structures was confirmed by a small-angle X-ray diffraction study and cross-section transmission electron microscope for films with Fe layer thicknesses >45 Å. In an Fe/MgF₂(9 Å/30 Å) sample, an island structure for the Fe layers was suggested by the existence of superparamagnetism in a film. At 4.2 K, enhancements of both magnetization and hyperfine field were observed in films having Fe layers thinner than 40 Å. The maxima in the magnetization (233 emu/g of Fe) and in the average hyperfine field (390 kOe) at 4.2 K were found in an Fe/MgF₂(9 Å/30 Å) film and were approximately 105% and 115% that of the bulk α-Fe, respectively. The thickness dependence suggests a 12% enhancement in the magnetic moment of interface Fe atoms. No exchange bias was found in the films, implying that antiferromagnetic fluorides are not formed at the interface, which is different from the case of Fe/LiF and Fe/CaF₂ multilayers.     

Interaction of HNCO with Au(111) surfaces

The surface chemistry of isocyanic acid, HNCO, and its dissociation product, NCO, was studied on clean, O-dosed and Ar ion bombarded Au(111) surfaces. The techniques used are high resolution energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD). The structure of Ar ion etched surface is explored by scanning tunneling microscopy (STM). HNCO adsorbs molecularly on Au(111) surface at 100 K yielding strong losses at 1390, 2270 and 3230 cm^? 1. The weakly adsorbed HNCO desorbs in two peaks characterized by T_p = 130 and 145 K. The dissociation of the chemisorbed HNCO occurs at 150 K to give NCO species characterized by a vibration at 2185 cm^? 1. The dissociation process is facilitated by the presence of preadsorbed O and by defect sites on Au(111) produced by Ar ion bombardment. In the latter case the loss feature of NCO appeared at 2130 cm^? 1. Isocyanate on Au(111) surface was found to be more stable than on the single crystal surfaces of Pt-group metals. Results are compared with those obtained on supported Au catalysts.     

Magnetic structure of the GdAl3 intermetallic compound as seen via Mössbauer spectroscopy data for 119Sn impurity atoms

The magnetic hyperfine interaction for ¹¹⁹Sn impurity atoms in GdAl₃ frustrated antiferromagnetic compound has been investigated by Mössbauer spectroscopy technique. Two magnetic subspectra with the ratio of the intensities 2:1 were observed. At 4.5 K, the values of the magnetic hyperfine field are 4.00(2) and 1.35(2) T. The peculiarities of the Mössbauer spectrum provide an opportunity to propose a plausible model of the spin arrangement in the GdAl₃ lattice. In each GdAl₃ basal layer, the magnetic moments of the Gd atoms form three-sublattice 120° spin structure that is peculiar to magnetically frustrated compounds. The appearance of two magnetically nonequivalent Sn sites is a result of vector summation of the transferred polarizations from Gd moments located in two adjacent GdAl₃ planes. The anomalous temperature behavior of the hyperfine field is characteristic of frustrated systems with competing exchange interactions.     

Characterization of Rh,Mo and Rh–Mo particles formed on TiO2(110) surface: A TDS,AES and RAIRS study

The structural and chemical characterization of Rh, Mo and Rh–Mo nanosized clusters formed by physical vapor deposition on TiO₂ single crystal was performed by Auger Electron Spectroscopy (AES), Thermal Desorption Spectroscopy (TDS) and Reflection Absorption Infrared Spectroscopy (RAIRS), applying CO as test molecule. On a slightly reduced titania surface 2D-like growth of Rh was revealed at 300 K up to 0.23 ML coverage by AES and CO-desorption experiments. For CO-saturated Rh particles TDS showed molecular CO desorption in a broad temperature range with T_p = 400, 440, 490 and 540 K (α-states), the latter state appearing only on the smallest Rh particles. The population of γ-state (T_p = 780–820 K) originating from the recombination of C and O atoms on the support began at Θ_Rh = 0.23ML and was maximized at around 1–2 ML Rh coverage, corresponding to 30% dissociation of CO. A possible dissociation precursor on Rh particles is identified as linearly bonded CO on step sites characterized by ν(C–O) of 2017 cm^? 1. Deliberation of CO₂ could not be detected between 170 and 900 K, showing the absence of disproportionation reaction. Instead of oxidizing CO molecules, oxygen atoms stemming from the dissociation of CO attached to the reduced centers of titania, indicating the role of adsorption sites at the perimeter of Rh particles in the decomposition process. 2 ML of predeposited Mo enhanced markedly the dispersion of Rh particles as a result of strong Rh–Mo interaction, but it slightly reduced the molecular α-CO desorption possibly due to enhanced dissociation. The formation of γ-CO was suppressed considerably through elimination of adsorption centers by Mo on the TiO₂ substrate. The reactivity of Rh layers deposited on Mo-covered surface towards CO was reduced after repeated annealing to 600 K due to partial encapsulation of Rh by titania, manifesting in the suppression of the more strongly bonded α-state. Mo-deposits (up to 0.5ML) on Rh particles decreased the saturation coverage of α-CO through a site-blocking mechanism without detectable influence on the binding energy of CO to Rh, indicating Mo island formation. The carbon arising from the decomposition of CO dissolved in the Mo-containing particles formed a solid solution stable even at 900 K, suggesting a possible role of molybdenum carbide regarding the enhanced catalytic activity of Rh clusters.