An investigation of the effect of pre-dosed O atoms on the adsorption of NO on Pt{2 1 1}

Reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to investigate the effect of pre-dosed O atoms on the adsorption of NO on Pt{2 1 1} at room temperature. RAIRS experiments show that no new species are formed when NO is adsorbed onto a Pt{2 1 1} surface that has been pre-dosed with oxygen and no species are lost from the spectra, compared to spectra recorded for NO adsorption on the clean Pt{2 1 1} surface. However pre-dosed oxygen atoms do influence the frequency and intensity of several of the observed infrared bands. In stark contrast, pre-dosed O has a large effect on the TPD spectra. In particular N₂ and N₂O desorption, seen following NO adsorption on the clean Pt{2 1 1} surface, is completely inhibited. This effect has been assigned to the blocking of NO dissociation by the pre-adsorbed O atoms. A new NO desorption peak, not seen for NO adsorption on the clean Pt{2 1 1} surface, is also observed in TPD spectra recorded following NO adsorption on an oxygen pre-dosed Pt{2 1 1} surface.     

Interaction of NO with the O-rich RuO2(1 1 0) surface at 300 K

The interaction of NO with the O-rich RuO₂(1 1 0) surface, exposing coordinatively unsaturated O-bridge, O-cus, and Ru-cus atoms, was studied at 300 K by thermal desorption spectroscopy (TDS) and high-resolution electron energy-loss spectroscopy (HREELS). The conclusions are validated by isotope substitution experiments with ¹⁸O. During exposure to NO an O···N–O surface group (NO₂-cus) is formed with O-cus. Additionally, a smaller number of empty Ru-cus sites are filled by NO-cus. If one warms the sample to 400 K, NO₂-cus does not desorb but decomposes into O and NO again, the latter being either released into gas phase or adsorbed as NO-cus. With O-bridge such a surface group is not stable at 300 K. Our experiments further prove that O-cus is more reactive than O-bridge.     

Optical characterization of methanol adsorption on the bare and oxygen precovered Cu(1 1 0) surface

We have studied the adsorption and reaction of methanol on the bare and oxygen precovered Cu(1 1 0) surface at 200 K using reflectance difference spectroscopy (RDS). On the bare and fully oxygen covered surface, the sticking coefficient is close to zero. In contrast, on the partially oxygen covered surface, a sticking coefficient close to unity is obtained. This observation suggests a high mobility of methanol on both bare and oxygen covered Cu(1 1 0) and of methoxy on Cu(1 1 0). Two reaction regimes, an oxygen supply limited and an adsorption site limited regime are identified. The transition between these two regimes occurs for an oxygen coverage of about 0.2.     

Interaction of atomic H and CO with Cu(1 1 0) and bimetallic Ni/Cu(1 1 0)

Co-adsorption of hydrogen and CO on Cu(1 1 0) and on a bimetallic Ni/Cu(1 1 0) surface was studied by thermal desorption spectroscopy. Hydrogen was exposed in atomic form as generated in a hot tungsten tube. The Ni/Cu surface alloy was prepared by physical vapor deposition of nickel. It turned out that extended exposure of atomic hydrogen leads not only to adsorption at surface and sub-surface sites, but also to a roughening of the Cu(1 1 0) surface, which results in a decrease of the desorption temperature for surface hydrogen. Exposure of a CO saturated Cu(1 1 0) surface to atomic H leads to a removal of the more strongly bonded on-top CO (α₁ peak) only, whereas the more weakly adsorbed CO molecules in the pseudo threefold hollow sites (α₂ peak) are hardly influenced. No reaction between CO and H could be observed. The modification of the Cu(1 1 0) surface with Ni has a strong influence on CO adsorption, leading to three new, distinct desorption peaks, but has little influence on hydrogen desorption. Co-adsorption of H and CO on the Ni/Cu(1 1 0) bimetallic surface leads to desorption of CO and H₂ in the same temperature regime, but again no reaction between the two species is observed.     

Oxygen on Fe(1 1 0): magnetic properties of the adsorbate system

Investigations concerning the electronic and magnetic properties of oxygen adsorbed on magnetized iron films were carried out by means of angle and spin resolving photoelectron spectroscopy. Iron(1 1 0), epitaxially grown on a W(1 1 0) crystal, served as the ferromagnetic substrate. Exchange splittings of the O 2p_x derived level were detected demonstrating a magnetic coupling between the chemisorbate and the iron layer. This observation indicates the presence of an induced magnetic moment within the adsorbate overlayer. Variations of the exchange splitting occurred as a function of the oxygen coverage, energy of the exciting radiation, and detection angle of the emitted photoelectrons pointing to a k₆-dependent exchange splitting. High oxygen exposures lead to a FeO overlayer at the surface, showing vanishing peak separations due to the antiferromagnetic behavior of iron oxide.     

Yttrium segregation and surface phases of yttria-stabilized zirconia (1 1 1) surface

Surface segregation of yttria-stabilized zirconia (YSZ) was studied via first-principles computations and thermodynamics. For the cubic YSZ (1 1 1) surface, yttrium can segregate only to a subsurface layer, and these segregation phases are terminated at the surface by defective oxygen layers with honeycomb structure. The segregation is independent of the bulk yttrium concentration at high oxygen partial pressures or low temperatures. At very low oxygen partial pressures and high temperatures there is no surface yttrium segregation and the surface is terminated by O–Zr. Our results provide a reasonable explanation for previous experimental work, and also a framework for extending our understanding of cation segregation in oxide surfaces.     

Acetaldehyde photochemistry on TiO2(1 1 0)

The ultraviolet (UV) photon induced decomposition of acetaldehyde adsorbed on the oxidized rutile TiO₂(1 1 0) surface was studied with photon stimulated desorption (PSD) and thermal programmed desorption (TPD). Acetaldehyde desorbs molecularly from TiO₂(1 1 0) with minor decomposition channels yielding butene on the reduced TiO₂ surface and acetate on the oxidized TiO₂ surface. Acetaldehyde adsorbed on oxidized TiO₂(1 1 0) undergoes a facile thermal reaction to form a photoactive acetaldehyde–oxygen complex. UV irradiation of the acetaldehyde–oxygen complex initiated photofragmentation of the complex resulting in the ejection of methyl radical into gas phase and conversion of the surface bound fragment to formate.     

Reaction of tert-butyl isocyanate and tert-butyl isothiocyanate at the Ge(100) − 2 × 1 Surface

The adsorption of tert-butyl isothiocyanate and tert-butyl isocyanate at the Ge(100) ? 2 × 1 surface was probed using multiple internal reflection Fourier transform infrared (FTIR) spectroscopy X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) modeling. Results indicate that there are multiple surface products for each molecule. FTIR studies of tert-butyl isothiocyanate reveal adsorption through an S-dative bonded state, while XPS studies further suggest a reactive desorption product which leaves excess sulfur atoms at the surface. Studies of tert-butyl isocyanate indicate that the molecule dissociatively adsorbs at the surface, resulting in tert-butyl and germyl isocyanate groups, as the major pathway, in addition to forming several minor products, including a [2 + 2] cycloaddition product across the C=N bond. DFT was used to simulate vibrational spectra and map the reaction pathways, and confirms that the assigned products are energetically favorable.     

Metallization of Ge(0 0 1)-p(2 × 1) surface as result of thermal fluctuations

We present a theoretical study of the metallization of Ge(0 0 1)-p(2 × 1) surface which is observed in experimental data. We have considered the connection between thermal fluctuation of this surface structure and its metallic properties. To this end we have performed long-time MD-DFT simulations. The obtained results show that thermal fluctuation of the Ge(0 0 1)-p(2 × 1) structure may cause its metallization which in not necessary connected with a flip-flop motion of dimer atoms. It was shown that the metallization of the Ge(0 0 1)-p(2 × 1) surface takes place when the dimer buckling angle is reduced to around 11°. In the case of our simulations the considered surface system remained in the metallic state for 25% of the simulation time. We have also found that the metallic state of the fluctuating Ge(0 0 1)-p(2 × 1) surface is built up by dangling bonds of the dimer atoms shifted up (D_up) and down (D_down).     

The electron stimulated chemistry of methyl lactate on Cu(1 1 1)

The electron stimulated chemistry of monolayers of (R)/(S)-methyl lactate ((S)/(R)-MLAc) adsorbed on Cu(1 1 1) has been investigated. Monolayers of MLAc undergo highly efficient electron stimulated processes predominately desorption, but also a significant fraction is converted to an adsorbed alkoxide moiety through the selective cleavage of the O–H bond. The efficiency of the depletion of the adsorbed MLAc state and the absence of significant non-selective fragmentation contrasts with previous studies of the electron beam irradiation of monolayers of oxygen containing organic molecules.     

Observation of hydrogen adsorption on 6H-SiC(0 0 0 1) surface

We have used coaxial impact-collision ion scattering spectroscopy (CAICISS) and time-of-flight elastic recoil detection analysis (TOF-ERDA) to investigate the adsorption of atomic hydrogen on the 6H-SiC(0 0 0 1)√3×√3 surface. It has been found that the saturation coverage of hydrogen on the 6H-SiC(0 0 0 1)√3×√3 surface is about 1.7 ML. Upon saturated adsorption of atomic hydrogen, the √3×√3 surface structure changes to the 1×1 structure. The data of the CAICISS measurements have indicated that as a result of the hydrogen adsorption, Si adatoms on the √3×√3 surface move from T₄ to on-top sites.     

Hydrogen sorption sites in holmium silicide on silicon(1 1 1)

The hydrogen sorption sites on the surface of holmium silicide grown on Si(1 1 1) have been determined using metastable de-excitation spectroscopy, ultraviolet photoemission spectroscopy and density functional theory calculations. Comparison of calculated and measured surface density of states spectra allow us to locate the position of the second subsurface hydrogen atom in each unit cell to an interstitial site in the layer of rare earth atoms. The hydrogenation energies indicate a reaction pathway that involves concomitant site occupation.     

Adsorption behaviors of CO on W(1 1 0) and Mo(1 1 0) surfaces in the β-state are still not clear

Adsorption structure of CO on W and Mo at above ～800 K (β-CO) has been extensively studied in the history of surface science. Most of the previous studies concluded that CO is dissociated in the β-CO, and a tilted structure plays a role as a precursor state of the dissociation. We have recently studied valence band spectra of the β-CO on W(1 1 0), oxygen-precovered W(1 1 0) and Mo(1 1 0) using synchrotron radiation. CO-derived states with binding energies close to those of the 4σ-CO can be observed, implying a non-dissociative chemisorption in this high-temperature state. We suggest that still some additional works need to be done in order to understand adsorption structure of β-CO completely.     

Epitaxial growth of well-ordered ultra-thin Al2O3 film on NiAl (1 1 0) by a single-step oxidation

Well-ordered ultra-thin Al₂O₃ films were grown on NiAl (1 1 0) surface by exposing the sample at various oxygen absorption temperatures ranging from 570 to 1100 K at dose rates 6.6 × 10⁻⁵ and 6.6 × 10⁻⁶ Pa. From the results of low-energy electron diffraction (LEED), Auger electron spectrometer (AES) and X-ray photon spectroscopy (XPS) observations, it was revealed that oxidation mechanism above 770 K is different from well-known two-step process. At high temperature, oxidation and crystallization occurred simultaneously while in two-step process oxidation and crystallization occurred one after another. At high-temperature oxidation well-ordered crystalline oxide can be formed by a single-step without annealing. Well-ordered Al₂O₃ layer with thickness over 1 nm was obtained in oxygen absorption temperature 1070 K and a dose rate 6.6 × 10⁻⁶ Pa at 1200 L oxygen.     

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.     

Investigation of the doped transition metal promotion effect on CO2 chemisorption on Ni (1 1 1)

The chemisorption of CO₂ on the pure Ni (1 1 1) and doped Ni (1 1 1) by transition metal (Co, Rh, Cr, Ce, La) were investigated by using the generalized gradient approximation (GGA) and the Perdew–Burke–Emzerhof (PBE) functional. The optimized structure of doped metal surface showed that Rh, Cr, Ce, La atoms upward shift from the surface of Ni (1 1 1) plane, while the atom radius of Co is the minimum offset which lead to the height is ?0.03 Å. The ability of CO₂ chemisorption follows the order of La/Ni (1 1 1) > Ce/Ni (1 1 1) > Cr/Ni (1 1 1) > Co/Ni (1 1 1) > pure Ni (1 1 1). It is exothermic when CO₂ chemisorbed on Cr/Ni (1 1 1) Ce/Ni (1 1 1) and La/Ni (1 1 1), while it is endothermic on the Co/Ni (1 1 1) and pure Ni (1 1 1). CO₂ molecular chemisorbed on all the metal surfaces are negatively charged, result from the electron transfer between the metal surfaces and the CO₂ molecular. The transition metals La, Ce and Cr can promote the transformation of electron and make the CO bonds longer than the pure Ni (1 1 1). We also analyzed the dissociation of CO₂ on the Ni-based surface and found that the La/Ni (1 1 1) surface is the preference surface for the dissociation of CO₂, which improved the ability to hinder carbon deposition.     

Preparation and characterization of Fe3O4(1 1 1) nanoparticles and thin films on Au(1 1 1)

Fe₃O₄ nanoparticles and thin films were prepared on the Au(1 1 1) surface and characterized using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Fe₃O₄ was formed by annealing α-Fe₂O₃(0 0 0 1) structures on Au(1 1 1) at 750 K in ultrahigh vacuum (UHV) for 60 min. Transformation of the α-Fe₂O₃(0 0 0 1) structures into Fe₃O₄ nanoparticles and thin films was supported by XPS. STM images show that during the growth procedure used, Fe₃O₄ initially appears as nanoparticles at low coverages, and forms thin films at ～2 monolayer equivalents (MLE) of iron. Two types of ordered superstructures were observed on the Fe₃O₄ particles with periodicities of ～50 and ～42 Å, respectively. As the Fe₃O₄ particles form more continuous films, the ～50 Å feature was the predominant superstructure observed. The Fe₃O₄ structures at all coverages show a hexagonal unit cell with a ～3 Å periodicity in the atomically resolved STM images.     

Adsorption of ZnO, (ZnO)2 and (ZnO)3 on MgO(0 0 1)

We have investigated the adsorption of ZnO, atomic Zn, atomic O and (ZnO)_n on the flat MgO(0 0 1) surface by means of density functional calculations. A single ZnO molecule prefers to bind in a position parallel to the surface with the zinc atom above a surface oxygen atom and the oxygen above a magnesium atom. Adsorption of a pair of ZnO molecules leads to the formation of (ZnO)₂ on the surface with geometric parameters slightly distorted from those of the free molecule, providing an indication of surface interaction with the adsorbate. Finally, the trimer forms on the surface with the same general shape as the gas phase trimer, but with angular distortions influenced by surface-molecule interactions. The effects of increasing surface coverage are also explored.     

Simulation of the first stage of oxide formation on Al(1 1 1)

At room temperature, the oxide formation on Al(1 1 1) starts on the boundaries of relatively large islands containing about or more than 20 chemisorbed oxygen atoms. We show that this special feature can be rationalized by assuming that the jump rate of oxygen atoms to the subsurface layer depends on lateral oxygen–oxygen interactions in the ground and activated states. In both cases, the lateral interaction is considered to consist of two components, including attractive nearest-neighbour interaction and repulsive elastic interaction at longer distances. To explain the experimentally observed details of oxide nucleation, the attractive interaction in the activated state should be slightly weaker than in the ground state.     

Oxygen adatoms at SrTiO3(0 0 1): A density-functional theory study

We present a density-functional theory study addressing the energetics and electronic structure properties of isolated oxygen adatoms at the SrTiO₃(0 0 1) surface. Together with a surface lattice oxygen atom, the adsorbate is found to form a peroxide-type molecular species. This gives rise to a non-trivial topology of the potential energy surface for lateral adatom motion, with the most stable adsorption site not corresponding to the one expected from a continuation of the perovskite lattice. With computed modest diffusion barriers below 1 eV, it is rather the overall too weak binding at both regular SrTiO₃(0 0 1) terminations that could be a critical factor for oxide film growth applications.