Probing the interactions of Pt, Rh and bimetallic Pt-Rh clusters with the TiO2(1 1 0) support

Pt, Rh, and Pt-Rh clusters on TiO₂(1 1 0) have been investigated by scanning tunneling microscopy (STM), soft X-ray photoelectron spectroscopy (sXPS), and low energy ion scattering (LEIS). The surface compositions of Pt-Rh clusters are Pt-rich (66-80% Pt) for room temperature deposition of both 2 ML of Pt on 2 ML of Rh (Rh + Pt) and 2 ML of Rh on 2 ML of Pt (Pt + Rh). Pt and Rh atoms readily diffuse within the clusters at room temperature, and although diffusion is slower at 240 K, intermixing of Pt and Rh still occurs. The binding energies of surface and bulk states for Rh(3d_5/2) and Pt(4f_7/2) can be distinguished in sXPS studies, and an analysis of these spectra indicates that the surface compositions of the Pt + Rh and Rh + Pt clusters are similar at room temperature but not identical. In addition to sintering, the pure Pt, pure Rh and Pt-Rh clusters become completely encapsulated by titania upon heating to 700 K. sXPS investigations show that annealing the clusters to 850 K induces reduction of titania support to Ti⁺² and Ti⁺³, with the extent of reduction being the greatest for Pt, the least for Rh and intermediate for Pt-Rh. We propose that TiO₂ is reduced at the metal-titania interface on top of the clusters, not at the base of the clusters. Furthermore, the extent of titania reduction is greater for metal clusters with weaker metal-oxygen bonds because oxygen atoms are less likely to migrate to the top of the clusters, and therefore the encapsulating titania is oxygen-deficient.     

Computational studies of the interactions between emeraldine and palladium atom

The structural end electronic properties of emeraldine base (EB) dimers interacting with a single Pd atom is investigated within Hartree-Fock with 6-31g(d, p) basis set for non-metal atoms, and 3-21g for Pd. It was found that Pd⁰ might create a stable complex with EB fragments. The influence of the Pd presence on the electronic structure of EB dimers is examined through an analysis of the total density of states and the crystal orbital overlap population (COOP).     

Theoretical studies on the interaction of oleoyl sarcosine with the surface of apatite

Quantum chemical methods were used to study interactions of models of oleoyl sarcosine (N-oleoyl-N-methyl-amino carboxylic acid) with the Ca²⁺ ion and the surface calcium of apatite. Geometry optimizations revealed that oleoyl sarcosine can form either bidentate or tridentate structures with Ca²⁺ ions. Modification of the functional group in the sarcosine model to investigate its influence on the interaction energies showed that the interaction energies vary with the group. Comparison of interactions of the Ca²⁺ ions and the surface calcium of apatite showed the interaction energies to change with the functional group in a similar way.     

Cu adsorption on pyrite (1 0 0): Ab initio and spectroscopic studies

Surface optimised S 2p photoelectron spectra show that both surface S²⁻ monomers and (S-S)²⁻ dimers are present at pyrite (1 0 0) fracture surfaces. In order to determine which sulfur species are involved in Cu adsorption, fresh pyrite surfaces were exposed to Cu²⁺ in solution. The S 2p spectra suggest that both types of S surface species are involved in the mechanism of Cu adsorption (activation). Ab initio density functional theory was used to model Cu adsorbed onto pyrite (1 0 0) to support the interpretation of the spectroscopy. Mulliken population analysis confirms the charge distribution suggested by the core line shifts as observed in the photoelectron spectra. The ab initio calculations were consistent with a two-coordinate bond between Cu(I), a surface S monomer and a surface S dimer.     

Photoelectron binding energy shifts observed during oxidation of group IIA,IIIA and IVA elemental surfaces

An extensive re-evaluation of XPS binding energies (BE's) and binding energy shifts (ΔBE's) from metals, oxides and the carbonates of the group II, III and IVA elements (exceptions are Be, Mg and Hf) has been carried out using a substrate specific BE referencing approach. From this, O-1s BE's are found to fall into surface oxide, bulk oxide and carbonate groupings, with bulk oxides showing the lowest BE's followed by surface oxides (+∼1.5 eV) and then carbonates (+∼3.0 eV). The O-1s BE's from the bulk oxides also appear to scale with 1/d, where d is inter-atomic distance. The same is noted in the ΔBE's observed from the metallic counterparts during oxidation of the elemental surfaces. This, and the decreasing BE exhibited by Ca, Sr and Ba on oxidation is explained within the charge potential model as resulting from competing inter- and intra-atomic effects, and is shown to be consistent with partial covalency arguments utilizing Madulung potentials. The ΔBE's also fall into groups according to the elements location in the periodic table, i.e. s, p or d block. These trends open up the possibility of approximating ΔBE's arising from initial and final state effects, and bond distances.     

Formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys

The formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys were investigated by X-ray photoelectron spectroscopy (XPS) and by adsorption of CO probe molecules, which was characterized by temperature-programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The PdAg/Pd(1 1 1) surface alloys were prepared by annealing (partly) Ag film covered Pd(1 1 1) surfaces, where the Ag films were deposited at room temperature. Surface alloy formation leads to a modification of the electronic properties, evidenced by core-level shifts (CLSs) of both the Pd(3d) and Ag(3d) signal, with the extent of the CLSs depending on both initial Ag coverage and annealing temperature. The role of Ag pre-coverage and annealing temperature on surface alloy formation is elucidated. For a monolayer Ag covered Pd(1 1 1) surface, surface alloy formation starts at ∼450 K, and the resulting surface alloy is stable upon annealing at temperatures between 600 and 800 K. CO TPD and HREELS measurements demonstrate that at 120 K CO is exclusively adsorbed on Pd surface atoms/Pd sites of the bimetallic surfaces, and that the CO adsorption behavior is dominated by geometric ensemble effects, with adsorption on threefold hollow Pd₃ sites being more stable than on Pd₂ bridge sites and finally Pd₁ a-top sites.     

Photoemission studies of the interactions of CdTe and Te with Si(100)

The interactions between CdTe, and in particular Te, and the (100) surface of Si have been probed using photoemission and low energy electron diffraction with a view to investigating the mechanisms responsible for (100) and (111) growth orientations for CdTe on Si(100). The interfacial reactions have been studied both on room temperature deposition followed by annealing and on depositions at typical epitaxial growth temperatures. In both cases the same precursor stage of an ordered submonolayer of Te on the Si(100) surface has been identified. Line shape analysis of the Si 2p core level has suggested a structural model in which Te adatoms make up an incomplete monolayer bound in bridge sites. This model is in excellent agreement both with the (1 × 1) LEED pattern and recent SEXAFS studies of this surface. The implications of the cubic symmetry of this surface in terms of the subsequent growth orientation of CdTe are discussed. Termination of the surface by Te was also seen to induce band bending suggestive of Fermi level pinning at around midgap, in contrast to the passivating behaviour of other group VI elements on this surface. The Si 2p core level line shape analysis on termination by Te has also provided evidence to support the “covalent dimer” interpretation of the clean dimerised Si(100) surface.     

Density functional theory study of hydrogen sulfide dissociation on bi-metallic Ni-Mo catalysts

This work presents results on the dissociation of H₂S over Ni-Mo catalysts suggesting that the presence of surface Mo-atom(s) has a significant impact on both the energetics of the process and the reaction mechanism. The presence of one Mo atom provides an additional energetic advantage of 10.2 kcal/mol overall. While increasing the energetic advantage of the process, the presence of Mo atom also increases the activation barriers by at most 3 kcal/mol. The large exothermic nature of this process combined with the comparatively small activation barriers suggests that the H₂S dissociation process is a facile process on all of the surfaces studied here. Additionally, analysis was provided to explain the difference in catalytic behavior between a bi-metallic alloy and a bi-metallic sulfide. It was determined that the bi-metallic alloy binds sulfur strongly (>100 kcal/mol) which can be compared with the results of Sun and co-workers [M. Sun, A.E. Nelson, J. Adjaye, Catal. Today 105 (2005) 36] who predict that S adsorption on the metal sulfide phase is not energetically favorable. It is suggested that the sulfide surface does not bind S in an energetically favorable manner because the sulfide surface structure does not possess a binding site that can emulate the hollow site on a metal surface.     

Theoretical study of CO2 activation on Pt(111) induced by coadsorbed K atoms

The adsorption of CO₂ on the clean and potassium-precovered Pt(111) surface has been studied by means of the cluster model approach within the hybrid B3LYP density functional theory-based method. On the clean surface, CO₂ is undistorted and weakly bound. The equilibrium position of this physisorbed species appears at a rather large distance from the surface. However, when coadsorbed K atoms are included in the model, a chemisorbed, bent CO₂ species on top of a surface Pt atom is found. The presence of the coadsorbed K is found to be necessary to promote CO₂ chemisorption and activation, the key step in activating the CO₂ molecule being a direct interaction with the coadsorbate. In addition, the calculated vibrational frequencies for this chemisorbed species are in agreement with available experimental data.     

Dissociative chemisorption of H2 on Pt(1 1 1): isotope effect and effects of the rotational distribution and energy dispersion

Six-dimensional quantum dynamics calculations on dissociative scattering of H₂ and D₂ from Pt(1 1 1) are performed. The six-dimensional potential energy surface used was generated using density functional theory employing the generalized gradient approximation. The isotope effect, the effect of widening the rotational distribution on the dissociation probability and the effect of the energy dispersion are investigated, as they are possible reasons for a discrepancy between previous theoretical work and molecular beam experiments. It was found that these effects cannot explain the differences between the theoretical and experimental results.     

Surface chemistry of alkyl and perfluoro ethers: a FTIR and ab initio study of adsorption and decomposition of CF3OCF3 on an Al2O3 surface

The adsorption and thermal decomposition of perfluorodimethyl ether, (CF₃)₂O, on a high-surface-area Al₂O₃ surface was investigated by FTIR under both vacuum and pressure conditions. IR spectra in the 4000-1050 cm⁻¹ range were collected and the spectral assignments were assisted by quantum chemical ab initio calculations. The spectral evidence indicated that (CF₃)₂O decomposed to form adsorbed fluoroformate, FCOO (ads). Increases of temperature (up to 525 K) caused the FCOO (ads) to convert to hydrogen formate, HCOO (ads). Surface hydroxyl groups participated in the decomposition of (CF₃)₂O and the conversion of FCOO (ads) to HCOO (ads). A decomposition mechanism is proposed.     

Theoretical study on the temperature-induced structural transition of the Si(1 1 3) surface

The temperature-induced structural transition of the Si(1 1 3) surface is investigated by ab initio calculations. In this study, it is found that the room-temperature phase and the high-temperature phase have the 3 × 2 interstitial structure and the 3 × 1 interstitial structure, respectively. The existence of the 3 × 2 and 3 × 1 interstitial structures is supported by the analysis of scanning tunneling microscopy (STM) images and the calculation of surface core level shifts using final state pseudopotential theory. The theoretical STM images of interstitial structures are in good agreement with the STM images suggested by experiments. The analysis of STM images provides an insight into the characteristics of domain boundaries observed frequently in experiments. It is also found that the domain boundary can be formed by local 3 × 1 interstitial structures on the 3 × 2 interstitial surface. The theoretical analysis of the surface core level shifts reveals that the surface core levels in experiment originate from the interstitial structures. The lowest values in the surface core level shifts are found to be associated with the 2p core level shifts of the interstitial atoms.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

Fabrication of model Pt-ceria catalysts and an analysis of their performance for CO oxidation

Model Pt-ceria catalysts have been prepared by the evaporation of Pt onto ceria (CeO₂) films grown on Si(1 1 1) substrates. Photoelectron spectroscopy (XPS, UPS) data are used to characterise the surfaces and their adsorption characteristics, and CO oxidation has been used as a probe reaction to test the activity of the model catalysts.Pure ceria is catalytically-inactive under the test conditions employed, whereas the model Pt/ceria catalysts demonstrate high activity for CO oxidation. The model catalysts also reproduce many of the characteristics of their high-surface area analogues, including the possession of a characteristic light-off temperature, hysteresis in activity as a function of temperature and a negative-order dependence on the CO partial pressure.Many aspects of the behaviour of these catalysts are shown to be a direct result of the strong adsorption of CO. The sensitivity of the dispersed Pt towards oxidation is also experimentally-demonstrated and the importance of this phenomenon is discussed.     

Carbon dioxide activation and alkali compound formation. I. Vibrational characterization of oxalate intermediates

The activation of CO₂ in thin potassium layers adsorbed on Cu(1 1 1) has been studied with time-evolved Fourier transform-infrared reflection absorption spectroscopy. The growth of thin layers by reactive evaporation of potassium in a CO₂ atmosphere permits control of the K:CO₂ stoichiometry, which strongly affects the selectivity in the formation of intermediates and the decomposition pathways of the layer. Layers grown in a CO₂ rich atmosphere exhibit the preferential growth of stoichiometric potassium oxalate K₂C₂O₄ (D_2h). The molecular identity of oxalate with D_2h symmetry is confirmed by vibrational spectra utilizing isotopic substitution methods (¹³CO₂ and C¹⁸O₂) and by the use of isotopic mixtures of CO₂/C¹⁸O₂ and CO₂/¹³CO₂. A comparison of the isotope data with theoretical calculations gives an estimated OCO bond angle in oxalate of 132°. Far-IR spectra obtained with synchrotron radiation indicate the equivalent interaction of all oxygen atoms with the potassium. A comparison of the vibrational data with theoretical ab initio calculations confirms the structural model of an oxalate species that is bulk coordinated with no strong directional bonding and all oxygen atoms equally interacting with potassium.At medium and low CO₂:K ratios, very complex vibrational spectra are observed, indicating the formation of an oxalate surface species with C_2v symmetry in addition to D_2h⁻ oxalate, CO₂⁻ and CO₂²⁻ species.     

Atomic and electronic structure of the corundum (0001) surface: comparison with surface spectroscopies

The electronic structure and geometry of the Al-terminated corundum (0001) surface were studied using a slab model within the ab-initio Hartree-Fock technique. The distance between the top Al plane and the next O basal plane is found to be considerably reduced on relaxation (by 0.57 Å, i.e. by 68% of the corresponding interlayer distance in the bulk). An interpretation of experimental photoelectron spectra (UPS He I) and metastable impact electron spectra (MIES) is given using the calculated total density of states of the slab and the projections to the atoms, atomic orbitals, and He 1s floating atomic orbital at different positions above the surface. Calculated projected densities of states exhibit a strong dependence on the relaxation of surface atoms. The good agreement of simulated and experimental UPS and MIES spectra supports the correctness of calculated surface relaxation.     

Characterization and chemical behavior of submonolayer coverages of titania on a Pt foil

The interaction between submonolayer titania coverages and Pt foil has been studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). The submonolayer titania can be fully oxidized to TiO₂ at 923 K under 10⁻⁸ Torr O₂, and partially oxidized to TiO_x at lower oxidation temperatures. The oxidized surface can be reduced by annealing to 1000 K or higher, or by heating in H₂ at 823 K, or by interacting with surface carbon formed from acetone decomposition. Under certain conditions (e.g., hydrogen reduction at 923 K), the surface titania can be fully reduced to metallic Ti which diffuses into bulk Pt readily. The reduced metallic Ti can resurface when the surface is oxidized at 923 K. Both XPS and HREELS data indicate the existence of subsurface oxygen, which plays an important role for the diffusion of Ti into and out of the Pt foil. Although no special interfacial active sites were revealed by HREELS studies of adsorbed acetone and CO, some TPD and XPS data suggest the presence of sites active for acetone decomposition.     

Cluster and band structure ab initio calculations on the adsorption of CO on acid sites of the TiO2(110) surface

The interaction of CO with the cationic sites of the TiO₂(110) surface has been investigated with cluster models and band structure calculations. The analysis of Hartree-Fock and correlated wavefunctions has shown that CO adsorbs at a distance of 4.4–4.5 bohr and a binding energy of 0.7–0.8 eV at low coverage. The bond strength is determined by the CO polarization and the CO б-donation to the surface while the electrostatic attraction is almost exactly cancelled by the Pauli repulsion. The adsorption is accompanied by two important measurable features, a considerable blue shift of the CO vibrational frequency and an increase of the CO 5б ionization potential. Both these effects have been analyzed in detail. We found that the CO ω shift is largely due to a combination of the electrostatic Stark effect and of the repulsion occurring when the CO molecule stretches in the presence of the rigid surface. The change in the 1π–5б binding energies, on the other hand, has an entirely electrostatic origin. Neither the ω shift nor the 5б binding energy shift are determined by the б-donation mechanism. Nevertheless, the occurrence of a charge transfer from CO to the empty levels of the Ti centers is well documented by (a) the energy and dipole moment change associated to this mechanism, (b) the expectation value of a projection operator which measures the charge associated with a given orbital, and (c) the CO dynamic dipole moment. The same analyses also rule out the occurrence of a Ti-to-CO back donation.     

Adsorption and diffusion of a single Pt atom on γ-Al2O3 surfaces

Motivated to better understand the interactions between Pt and γ-Al₂O₃ support, the adsorption and diffusion of a single Pt atom on γ-Al₂O₃ was studied using density functional theory. Two different surface models with atoms of various coordination (3–5) were used, one derived from a defected spinel structure, and another derived from the dehydration of boehmite (AlOOH). Adsorption energies are similar for the two surfaces, about −2 eV for the most stable sites, and involve Pt binding to surface O atoms. An unusually strong trapping geometry whereby Pt moves into the surface was identified over the boehmite-derived surface. In all cases the surface transfers 0.2–0.3 e⁻ to the Pt atom. The bonding is explained as being a combination of charge transfer between the surface and Pt atom, polarization of the metal atom, and some weak covalent bonding. The similarity of the two surfaces is attributed to the similar local environments of the surface atoms, as corroborated by geometry analysis, density of states, and Bader charge analysis. Calculated activation barriers (0.3–0.5 eV) for the defected spinel surface indicate fast diffusion and a kinetic Monte Carlo model incorporated these barriers to determine exact diffusion rates and behavior. The kinetic Monte Carlo results indicate that at low temperatures (<500 K) the Pt atom can become trapped at certain surface regions, which could explain why the sintering process is hindered at low temperature. Finally we modeled the adsorption of Pt on hydrated surfaces and found adsorption to be weaker due to steric repulsion and/or decreased electron-donating ability of the surface.     

Vibrational study of silicon oxidation: H2O on Si(100)

The vibrational spectrum of water dissociatively adsorbed on Si(100) surfaces is obtained with surface infrared absorption spectroscopy. Low frequency spectra (< 1450 cm⁻¹ are acquired using a buried CoSi₂ layer as an internal mirror to perform external reflection spectroscopy. On clean Si(100), water dissociates into H and OH surface species as evidenced by EELS results [1] in the literature which show a Si---H stretching vibration (2082 cm⁻¹), and SiO---H vibrations (O---H stretch at 3660 cm⁻¹ and the Si---O---H bend and Si---O stretch of the hydroxyl group centered around 820 cm⁻¹). In this paper, infrared (IR) measurements are presented which confirm and resolve the issue of a puzzling isotopic shift for the Si---O mode of the surface hydroxyl group, namely, that the Si---O stretch of the O---H surface species formed upon H₂O exposure occurs at 825 cm⁻¹, while the Si---O stretch of the ---OD surface species formed upon D₂O exposure shifts to 840 cm⁻¹, contrary to what is expected for simple reduced mass arguments. The higher resolution of IR measurements versus typical EELS measurements makes it possible to identify a new mode at 898 cm⁻¹, which is an important piece of evidence in understanding the anomalous frequency shift. By comparing the results of measurements for adsorption of H¹⁶₂O, H¹⁸₂O and D₂O with the results from recently performed first-principles calculations, it can be shown that a strong vibrational interaction between the Si---O stretching and Si---O---H bending functional group vibrations of the hydroxyl group accounts for the observed isotopic shifts.