Adsorption of water on thin V2O3(0 0 0 1) films

V₂O₃(0 0 0 1) films have been grown epitaxially on Au(1 1 1) and W(1 1 0). Under typical UHV conditions these films are terminated by a layer of vanadyl groups as has been shown previously [A.-C. Dupuis, M. Abu Haija, B. Richter, H. Kuhlenbeck, H.-J. Freund, V₂O₃(0 0 0 1) on Au(1 1 1) and W(1 1 0): growth, termination and electronic structure, Surf. Sci. 539 (2003) 99]. Electron irradiation may remove the oxygen atoms of this layer. H₂O adsorption on the vanadyl terminated surface and on the reduced surface has been studied with thermal desorption spectroscopy (TDS), vibrational spectroscopy (IRAS) and electron spectroscopy (XPS) using light from the BESSY II electron storage ring in Berlin. It is shown that water molecules interact only weakly with the vanadyl terminated surface: water is adsorbed molecularly and desorbs below room temperature. On the reduced surface water partially dissociates and forms a layer of hydroxyl groups which may be detected on the surface up to T ∼ 600 K. Below ∼330 K also co-adsorbed molecular water is detected. The water dissociation products desorb as molecular water which means that they recombine before desorption. No sign of surface re-oxidation could be detected after desorption, indicating that the dissociation products desorb completely.     

Low temperature adsorption of oxygen on reduced V2O3(0 0 0 1) surfaces

Well ordered V₂O₃(0 0 0 1) films were prepared on Au(1 1 1) and W(1 1 0) substrates. These films are terminated by a layer of vanadyl groups under typical UHV conditions. Reduction by electron bombardment may remove the oxygen atoms of the vanadyl layer, leading to a surface terminated by vanadium atoms. The interaction of oxygen with the reduced V₂O₃(0 0 0 1) surface has been studied in the temperature range from 80 to 610 K. Thermal desorption spectroscopy (TDS), infrared reflection absorption spectroscopy (IRAS), high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) were used to study the adsorbed oxygen species. Low temperature adsorption of oxygen on reduced V₂O₃(0 0 0 1) occurs both dissociatively and molecularly. At 90 K a negatively charged molecular oxygen species is observed. Upon annealing the adsorbed oxygen species dissociates, re-oxidizing the reduced surface by the formation of vanadyl species. Density functional theory was employed to calculate the structure and the vibrational frequencies of the O₂ species on the surface. Using both cluster and periodic models, the surface species could be identified as η²-peroxo () lying flat on surface, bonded to the surface vanadium atoms. Although the O-O vibrational normal mode involves motions almost parallel to the surface, it can be detected by infrared spectroscopy because it is connected with a change of the dipole moment perpendicular to the surface.     

A study of the interaction between perylene and the TiO2(1 1 0)-(1 × 1) surface-based on XPS, UPS and NEXAFS measurements

The interaction between a semi-large aromatic hydrocarbon compound (perylene) and the TiO₂(1 1 0)-(1 × 1) surface under ultra high vacuum conditions has been probed by X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) and near-edge X-ray absorption fine structure (NEXAFS) methods. UPS measurements of the adsorbate system have been compared with an experimental UPS spectrum of perylene in the gas phase and a calculated spectrum obtained by means of density functional theory (DFT) methods. NEXAFS results of perylene molecules adsorbed on TiO₂(1 1 0)-(1 × 1) were compared with data from an α-phase perylene single crystal. A novel analysis of the valence data has been employed to show that no strong chemical interaction takes place between perylene and the TiO₂(1 1 0)-(1 × 1) surface. Furthermore, angle-dependent NEXAFS measurements and the growth curve results suggest that the perylene molecules are oriented flat down onto the TiO₂ substrate due to weak van der Waals interactions.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

Reactivity of monolayer V2O5 films on TiO2(1 1 0) produced via the oxidation of vapor-deposited vanadium

The growth, and reactivity of monolayer V₂O₅ films supported on TiO₂(1 1 0) produced via the oxidation of vapor-deposited vanadium were studied using X-ray photoelectron spectroscopy and temperature programmed desorption (TPD). Oxidation of vapor-deposited vanadium in 10⁻⁷ Torr of O₂ at 600 K produced vanadia films that contained primarily V³⁺, while oxidation in 10⁻³ Torr at 400 K produced films that contained primarily V⁵⁺. The reactivity of the supported vanadia layers for the oxidation of methanol to formaldehyde was studied using TPD. The activity for this reaction was found to be a function of the oxidation state of the vanadium cations in the film.     

XPS and UPS study of Na deposition on thin film V2O5

The deposition of Na on thin film V₂O₅ has been study by using photoelectron spectroscopy. Vanadium ions are strongly reduced due to the deposition of Na. Three kinds of Na species were observed on the surface: the first is assigned to intercalated Na; the second is contributed to Na₂O₂; the third is appointed to metallic Na. The formation of Na₂O₂ leads to arise an emission line at about 10.3 eV in the valence band spectra. The metallic Na will further react with the oxides substrate and form Na₂O₂ on the surface in UHV chamber.     

Proline adsorption on TiO2(1 1 0) single crystal surface: A study by high resolution photoelectron spectroscopy

The surface chemistry and binding of dl-proline were investigated on the oxidised (stoichiometric) and reduced (sub-stoichiometric) TiO₂(1 1 0) single crystal surfaces. TiO₂ was chosen as the substrate as it best represents the surface of a biomedical implant, which bio-molecules interact with during the healing of bone/teeth fractures (molecular recognition). High resolution X-ray photoelectron spectroscopy (HR-XPS) studies of the C1s and N1s regions revealed that dl-proline is present in two forms (dissociated and zwitterionic) on the oxidised TiO₂ surface. On TiO₂(1 1 0) surfaces reduced by Ar⁺ sputtering, a significant increase in the amount of zwitterionic proline at the surface was detected when compared with the oxidised surface. Study of the temperature effect showed that in both cases the zwitterionic structure was the less stable structure. The reason for its relative instability appears to be thermodynamic.     

Room-temperature-adsorption behavior of acetic anhydride on a TiO2(1 1 0) surface

We have studied the adsorption structure of acetic anhydride on a TiO₂(1 1 0) surface using XPS (X-ray photoelectron spectroscopy), LEED (low energy electron diffraction) and HREELS (high resolution electron energy loss spectroscopy) to determine the origins of the unique adsorption properties of carboxylic acids on a TiO₂(1 1 0) surface. The C 1s XPS data indicated that the saturation carbon amount of adsorbed acetic anhydride was 12 ± 3% larger than that of the adsorbed acetic acid. LEED showed p(2 × 1) weak spots for the acetic anhydride adsorbed surface. The HREELS spectra revealed the dissociative adsorption of acetic anhydride. Based on these findings, we concluded that the neutralization of the bridging oxygen atoms associated with the dissociative adsorption is necessary for the stable adsorption of carboxylates on the 5-fold Ti sites.     

Growth of Al2O3 thin films on NiAl(1 0 0) by gas-phase oxidation and electro-oxidation

The growth and structures of aluminum oxides on NiAl(1 0 0) have been investigated by RHEED (reflection high energy electron diffraction), complemented by LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and STM (scanning tunneling microscopy). Crystalline θ-Al₂O₃ phase grows through gas-phase oxidation on the NiAl(1 0 0) substrate with its a and b-axes parallel to [0 −1 0] and [0 0 1] direction of the substrate, respectively, forming a (2 × 1) unit cell. Whilst, three-dimensional nano-sized NiAl(1 0 0) protrusions and Al₂O₃, NiAl(0 1 1) clusters were found to co-exit at the surface, evidenced by extraordinary transmission spots superposed to the substrate reflection rods in the RHEED patterns. Particularly, the NiAl(0 1 1) clusters develop with their (0 1 1) plane parallel to the NiAl(1 0 0) surface, and [1 0 0] axis parallel to the [0 −1 1] direction of the substrate surface. STM observation combined with information from AES and TPD (temperature programmed desorption) suggest the formation of these 3D structures is closely associated with partial decomposition of the crystalline oxides during annealing. On the other hand, smoother (2 × 1) oxide islands with thickness close to a complete monolayer of θ-Al₂O₃ can be formed on NiAl(1 0 0) by electro-oxidation, in contrast with the large crystalline films formed by gas-oxidation.     

Formamide reactions on rutile TiO2(0 1 1) surface

The reaction of formamide over the (0 1 1) faceted TiO₂(0 0 1) surface has been studied by Temperature Programmed Desorption (TPD) and X-ray Photoelectron Spectroscopy (XPS). Two main reactions were observed: dehydration to HCN and H₂O and decomposition to NH₃ and CO. The dehydration reaction was found to be three to four times larger than the decomposition at all coverages. Each of these reactions is found to occur in two temperature domains which are dependent upon surface coverage. The low temperature pathway (at about 400 K) is largely insensitive to surface coverage while the high temperature pathway (at about 500 K) shifts to lower temperatures with increasing surface coverage. These two temperature pathways may indicate two adsorption modes of formamide: molecular (via an η¹(O) mode of adsorption) and dissociative (via an η²(O,N) mode of adsorption). C1s and N1s XPS scans indicated the presence of multiple species after formamide absorption at 300 K. These occurred at ca. 288.5 eV (-CONH-) and 285 eV (sp³/sp² C) for the C1s and 400 eV-(NH₂), 398 eV (-NH) and 396 eV (N) for the N1s and result from further reaction of formamide with the surface.     

Scanning tunneling microscopy study of growth of Pt nanoclusters on thin film Al2O3/NiAl(1 0 0)

The growth of Pt nanoclusters on thin film Al₂O₃ grown on NiAl(1 0 0) was studied by using scanning tunneling microscopy (STM). The samples were prepared by vapor depositing various amounts of Pt onto the Al₂O₃/NiAl(1 0 0) at different substrate temperatures in ultra high vacuum (UHV). The STM images show that sizeable Pt nanoclusters grow solely on crystalline Al₂O₃ surface. These Pt clusters appear to be randomly distributed and only a few form evident alignment patterns, contrasting with Co clusters that are highly aligned on the crystalline Al₂O₃. The size distributions of these Pt clusters are rather broader than those of the Co clusters on the same surface and the sizes are evidently smaller. With increasing coverage or deposition temperature, the number of larger clusters is enhanced, while the size of the majority number of the clusters remains around the same (0.4 nm as height and 2.25 nm as diameter), which differs drastically from the Pt clusters on γ-Al₂O₃/NiAl(1 1 0) observed earlier. These Pt cluster growth features are mostly attributed to smaller diffusion length and ease to form stable nucleus, arising from strong Pt-Pt and Pt-oxide interactions and the peculiar protrusion structures on the ordered Al₂O₃/NiAl(1 0 0). The thermal stability of Pt nanoclusters was also examined. The cluster density decreased monotonically with annealing temperature up to 1000 K at the expense of smaller clusters but coalescence is not observed.     

Epitaxial MoOx nanostructures on TiO2(1 1 0) obtained using thermal decomposition of Mo(CO)6

Stoichiometric and highly-defective TiO₂(1 1 0) surfaces (called as yellow and blue, respectively) were exposed to Mo(CO)₆ vapours in UHV and in a reactive O₂ atmosphere. In the case of yellow-TiO₂, an O₂ reactive atmosphere was necessary to obtain the Mo(CO)₆ decomposition at 450 °C with deposition of MoO_x nanostructures where, according to core level photoemission data, the Mo⁺⁴ state is predominant. In the case of blue-TiO₂ it was possible to obtain Mo deposition both in UHV and in an O₂ atmosphere. A high dose of Mo(CO)₆ in UHV on blue-TiO₂ allowed the deposition of a thick metallic Mo layer. An air treatment of this sample at 580 °C led to the elimination of Mo as MoO₃ and to the formation of a transformed layer of stoichiometry of Ti_(1−x)Mo_xO₂ (where x is close to 0.1) which, according to photoelectron diffraction data, can be described as a substitutional near-surface alloy, where Mo⁺⁴ ions are embedded into the titania lattice. This embedding procedure results in a stabilization of the Mo⁺⁴ ions, which are capable to survive to air exposure for a rather long period of time. After exposure of the blue-TiO₂(1 1 0) substrate to Mo(CO)₆ vapours at 450 °C in an O₂ atmosphere it was possible to obtain a MoO₂ epitaxial ultrathin layer, whose photoelectron diffraction data demonstrate that is pseudomorphic to the substrate.     

Spectroscopic study on thermal reaction and desorption of sulfur/Rh(1 0 0) induced by oxygen-containing molecules

The surface reaction and desorption of sulfur on Rh(1 0 0) induced by O₂ and H₂O are investigated with X-ray photoelectron spectroscopy (XPS) technique. The Rh(1 0 0) sample covered with atomic sulfur is prepared by means of the exposure to H₂S gas, and subsequently the sample is annealed under O₂ or H₂O atmosphere. The XPS results show that atomic sulfur adsorbed on Rh(1 0 0) reacts with O₂ and desorbs from the surface at 473 K or more. On the other hand, atomic sulfur can not be removed from Rh(1 0 0) surface by H₂O at any temperature.     

Combined investigation of water sorption on TiO2 rutile (1 1 0) single crystal face: XPS vs. periodic DFT

XPS and periodic DFT calculations have been used to investigate water sorption on the TiO₂ rutile (1 1 0) face. Two sets of XPS spectra were collected on the TiO₂ (1 1 0) single crystal clean and previously exposed to water: the first set with photoelectrons collected in a direction parallel to the normal to the surface; and the second set with the sample tilted by 70°, respectively. This tilting procedure promotes the signals from surface species and reveals that the first hydration layer is strongly coordinated to the surface and also that, despite the fact that the spectra were recorded under ultra-high vacuum, water molecules subsist in upper hydration layers. In addition, periodic DFT calculations were performed to investigate the water adsorption process to determine if molecular and/or dissociative adsorption takes place. The first step of the theoretical part was the optimisation of a dry surface model and then the investigation of water adsorption. The calculated molecular water adsorption energies are consistent with previously published experimental data and it appears that even though it is slightly less stable, the dissociative water sorption can also take place. This assumption was considered, in a second step, on a larger surface model where molecular and dissociated water molecules were adsorbed together with different ratio. It was found that, due to hydrogen bonding stabilisation, molecular and dissociated water molecules can coexist on the surface if the ratio of dissociated water molecules is less than ≈33%. These results are consistent with previous experimental works giving a 10-25% range.     

Formation and characterization of Rh-Mo bimetallic layers on the TiO2(1 1 0) surface

The investigation of Rh, Mo and Rh-Mo nanosized clusters formed by physical vapor deposition on TiO₂(1 1 0) single crystal was performed by X-ray Photoelectron Spectroscopy (XPS), Low Energy Ion Scattering (LEIS) and Auger Electron Spectroscopy (AES). There was no sign for site-exchange between Mo and Rh atoms during deposition of Mo onto Rh particles at 330 K. Mixing between Ti and Mo ions was facilitated at the Mo particle-titania interface due to reaction at 550-700 K. The redox process between titania and Mo deposit was hindered at 330 K by forming predeposited rhodium layer (Θ_Rh = 2.0 ML), but reached nearly the same extent as without Rh after moderate heating to 600 K. The encapsulation of Rh by titania was complete by about 700 K in the presence of 1.2 ML Mo, in case of Mo-predeposition and Mo-postdeposition as well. Elevating the temperature of TiO₂/Rh-Mo layers above 700 K, these metals form alloy at the Mo-Rh interface irrespective of deposition sequences.     

Surface chemistry of NO and NO2 on the Pt(1 1 0)-(1 × 2) surface: A comparative study

The surface chemistry of NO and NO₂ on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N₂ and N₂O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO₂ decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO₂/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.     

Adsorption and reaction of methanethiol on the Ru(0 0 0 1)-p(2 × 2)O surface: A TPD and XPS study

Methanethiol adsorbed on Ru(0 0 0 1)-p(2 × 2)O has been studied by TPD and XPS. The dissociation of methanethiol to methylthiolate and hydrogen at 90 K is evidenced by the observation of hydroxyl and water. The saturation coverage of methylthiolate is ∼0.15 ML, measured by both XPS and TPD. A detailed analysis suggests that only the hcp-hollow sites have been occupied. Upon annealing the surface, water and hydroxyl desorb from the surface at ∼210 K. Methylthiolate decomposes to methyl radical and atomic sulphur via C-S cleavage between 350 and 450 K. Some methyl radicals (0.05 ML) have been transferred to Ru atoms before they decompose to carbon and hydrogen. The rest of methyl radicals desorb as gaseous phase. No evidence for the transfer of methyl radical to surface oxygen has been found.     

Adsorption structure of acetic anhydride on a TiO2(1 1 0) surface observed by scanning tunneling microscopy

The carboxylic acids are stably adsorbed on TiO₂(1 1 0) surfaces at room temperature. To demonstrate the neutralization mechanism proposed by Ashima et al. [H. Ashima, W.-J. Chun, K. Asakura, Surf. Sci. 601 (2007) 1822.] that explains the stable adsorption of carboxylic acids, we studied the full-coverage adsorption structure of acetic anhydride on a TiO₂(1 1 0) surface by STM (scanning tunneling microscopy). We directly observed three postulated species on the TiO₂(1 1 0) surface; normal acetates (termed acetate A) forming a (2 × 1) ordered structure, a minor acetate species (termed acetate B) which was present between the bridging oxygen and the 5-fold Ti, and the oxygen vacancies. We determined the ratio of these three species. This ratio was in good agreement with the postulated conversion reaction of acetate B to A.     

Adsorption and reactivity of SO2 on Ir(1 1 1) and Rh(1 1 1)

The adsorption and reactivity of SO₂ on the Ir(1 1 1) and Rh(1 1 1) surfaces were studied by surface science techniques. X-ray photoelectron spectroscopy measurements showed that SO₂ was molecularly adsorbed on both the Ir(1 1 1) surface and the Rh(1 1 1) surface at 200 K. Adsorbed SO₂ on the Ir(1 1 1) surface disproportionated to atomic sulfur and SO₃ at 300 K, whereas adsorbed SO₂ on the Rh(1 1 1) surface dissociated to atomic sulfur and oxygen above 250 K. Only atomic sulfur was present on both surfaces above 500 K, but the formation process and structure of the adsorbed atomic sulfur on Ir(1 1 1) were different from those on Rh(1 1 1). On Ir(1 1 1), atomic sulfur reacted with surface oxygen and was completely removed from the surface, whereas on Rh(1 1 1), sulfur did not react with oxygen.     

XPS study of SnTe(1 0 0) oxidation by molecular oxygen

The interaction between the (1 0 0) surface of SnTe single crystal and molecular oxygen was studied by means of X-ray photoelectron spectroscopy (XPS). Analysis of the obtained spectra shows that the mechanism of surface oxidation does not change in the range of oxygen exposure 10⁸-10¹³ L. During the oxidation an additional component shifted 1.1 eV towards higher binding energies appears in the Sn 3d spectra. The Te 3d_5/2 spectra fitting reveals two additional components with binding energies close to Te⁰ and Te⁺⁴. The dependence of the additional components fraction in both Sn 3d and Te 3d_5/2 spectra on the oxygen exposure is semi-logarithmic. On the base of the experimental data two possible mechanisms are proposed.