The formation of subsurface oxygen on Pt(100)

PhotoEmission Electron Microscopy (PEEM) enables imaging a surface via its work function. If a CO covered Pt(100) surface is exposed to oxygen patches are formed which appear dark in the PEEM image due to their high work function. As the surface is heated to temperatures above 650 K we observe the conversion of these dark islands into very bright ones with work functions much lower than even that of the clean surface. These findings are attributed to a change in the dipole moment of the adsorbed oxygen induced by their migration beneath the surface. A total work-function decrease of up to 1.2 eV has been evaluated independently using a Scanning Photoemission Microscope (SPM). The properties of this new kind of oxygen were also further investigated with thermal desorption spectroscopy and with Auger-electron spectroscopy.     

Water formation on oxygen exposure of some hydrides of intermetallic compounds

It is found that a large number of metal hydrides such as hydrides of materials in Ca−Mg−Ni can form water when exposed to O₂ largely without signs for concomitant substrate oxidation. One can speak of a catalytic reaction in this connection as the H-depleted metal matrix can in most cases be rehydrided and water synthesis repeated on exposure to O₂. In some cases a considerable portion of the H combustion reaction takes place in a matter of seconds. Some of the metal hydrides such as hydrides of CaNi₄B, CeNi₃, and YbNi₂, are relatively stable concerning decomposition of the alloy by the product water, while others, for example hydrides of CaNi₃, and CaNi₂, are rapidly decomposed by the product water forming the hydroxide of the electropositive metal. They also produce fine ferromagnetic Ni-particles which could be interesting for other catalytic purposes. Guest professor, work also performed at University of California at San Diego where support by a grant from DOE, Basic Energy Sciences, is acknowledged.     

Energy accommodation and reactivity of O2 on tungsten

We have determined by direct molecular beam velocity measurements that translational energy accommodation of O₂ molecules scattered from a hot polycrystalline tungsten target is inefficient at high surface temperatures. Translational energy accommodation is inefficient whether the surface is clean or covered with oxygen to a varying extent, even though in the latter case the scattering is diffuse. On a clean tungsten surface the scattering of the O₂ was approximately specular and the reaction probability of O₂ was constant and greater than 90% over the temperature range 1000K to 2800 K. It was shown by simultaneous helium scattering that atomic surface roughness of an oxygen chemilayer, rather than trapping, is a major cause of the observed diffuse scattering of oxygen. At the lowest surface temperature of 1000 K, with an oxygen chemilayer present, the velocity of the most probable number density of the scattered O₂ was lower than in the incoming beam or than that expected for complete equilibration with the surface.     

Laser-assisted reaction of metals with oxygen

The present status of experimental and theoretical work on continuous wave laser-assisted reaction of metals with oxygen is presented. Differences between this and normal isothermal oxidation of metals are emphasized. Available theoretical models are discussed. They deal with roles of thermal history, feedback effects between optical absorption and reaction rate. The nature of so-called non-purely thermal effects is discussed. Hints for further research are presented.     

Isotope effects in electron impact desorption of CO and O2 adsorbed on the (110) plane of tungsten

Results on the isotope effect for total and ionic desorption cross sections in the electron impact desorption of various binding states of CO on the (110) plane of tungsten, and of oxygen on this plane are presented and discussed. It is shown that the observations allow a dissection of cross sections into excitation cross sections and escape probabilities, and that the latter can be used to estimate lifetimes of excited or ionic states. It is found that excitation cross sections for total desorption are of the order of 10⁻¹⁶–10⁻¹⁷ cm², but seem to be significantly smaller in some cases for excitation to ionic states, suggesting that different excitations are involved. In all cases examined here the isotope effect for total desorption is much smaller than for ion production. This can be explained by the fact that ion lifetimes are somewhat shorter than those of excited neutrals. Lifetimes are estimated, in the cases examined, to be of the order of 10⁻¹⁴s.     

Laser-induced etching of titanium by Br2 and CCl3Br at 248 nm

A quartz crystal microbalance (QCM) has been used to study the KrF* excimer laser-induced etching of titanium by bromine-containing compounds. The experiment consists of focusing the pulsed UV laser beam at normal incidence onto the surface of a quartz crystal coated with 1 m of polycrystalline titanium. The removal of titanium from the surface is monitored in real time by measuring the change in the frequency of the quartz crystal. The dependence of the etch rate on etchant pressure and laser fluence was measured and found to be consistent with a two-step etching mechanism. The initial step in the etching of titanium is reaction between the etchant and the surface to form the etch product between laser pulses. The etch product is subsequently removed from the surface during the laser pulse via a laser-induced thermal desorption process. The maximum etch rate obtained in this work was 6.2 Å-pulse^–1, indicating that between two and three atomic layers of Ti can be removed per laser pulse. The energy required for desorption of the etch product is calculated to be 172 kJ-mole^–1, which is consistent with the sublimation enthalpy of TiBr₂ (168 kJ-mole^–1). The proposed product in the etching of titanium by Br₂ and CCl₃Br is thus TiBr₂. In the etching of Ti by Br₂, formation of TiBr₂ proceeds predominantly through the dissociative chemisorption of Br₂. In the case of etching with CCl₃Br, TiBr₂ is formed via chemisorption of Br atoms produced in the gas-phase photodissociation of CCl₃Br.     

Deactivation of TiO2 photocatalytic films loaded on aluminium: XPS and AFM analyses

TiO₂ films were loaded on aluminium substrates by dip-coating method. Based on cyclic photocatalytic degradation experiments using benzamide as model molecule, XPS and AFM tests, the deactivating behaviour of the samples was studied. Experiment results show that the samples with less coating times (one to four times) deactivated very quickly, while the samples coated more than five times did not lose activity. Al element was proved to segregate from substrate and diffuse into TiO₂ films during calcination and annealing treatment, existing as mixture of Al₂O₃ and Al(OH)₃ at the boundaries among TiO₂ particles. During photocatalytic reactions in aqueous phase, the transformation of Al from Al₂O₃ to Al(OH)₃ and the leaching of the latter brought out serious alternation of surface morphology to the samples coated one to three times, on whose surface Ti³⁺ and Ti²⁺ centers were also detected after six cycles of photocatalytic reactions, while fresh films and the tested films which did not deactivate possess unique +4 valence Ti. The alteration of surface morphology, together with the change of valence of surface Ti element, resulted in the deactivation encountered in this research.     

Infrared absorption of H2 adsorbed on porous glass,silica gel,and MgO

Infrared absorption of the vibrational band of H₂ in the bulk is known to arise from overlap and quadrupolar interactions. For adsorbed H₂, in addition to intermolecular interactions, an interfacial mechanism of inducing absorption has been identified in porous Vycor glass. A large enhancement of the fundamental vibrational line (by a factor of 60) from the bulk H₂ (liquid) has been observed. The vibrational overtone absorption is similarly enhanced by 150. We discuss these results as well as infrared absorption measurements for H₂ on MgO and silica gels.     

Study of non-radiative silicon deexcitation in an oxygen atmosphere using the differential measurement of the excited state lifetimes

Having developed a new method of differential lifetime measurement using atomic ionoluminescence as an excitation process, we applied this method to a monocrystaline silicon sample in an oxygen atmosphere of variable pressure. We found decreased values of the experimental lifetimes concerning levels 4s ³ P ⁰ and 4s ¹ P ⁰, which are more marked when the oxygen pressure increases. This tends then towards a saturation of the observed phenomenon. We propose, in agreement with other authors, an explanation which is based on the existence of non-radiative deexcitations. We present also a mathematical model for calculating this transition effect on the lifetime measurements. We consider that it is possible to take advantage of this experimental lifetime variation to determine a parameter of the model which characterises the non-radiative deexcitations. This measuring method appears to be a simple and original procedure for the study of certain nonradiative transitions.     

Precursor mediated and direct adsorption of molecular nitrogen on Fe{111}

In this article, we will summarize the kinetic models for nitrogen dissociation on Fe {111} and will present new data on the adsorption mechanism for the -bonded -N₂ state, which was identified as the immediate precursor for dissociation. Our results reveal that adsorption into the state can occur via the more weakly bonded state, but also by direct impact from the gas phase. The sticking coefficient via the state precursor depends directly on its concentration, and therefore depends on the temperature of the substrate and the gas pressure. Contrary to our previous estimates, the kinetic parameters for precursor mediated adsorption into the state in the limit of zero coveragecannot explain the high temperature dissociation probability. The direct channel from the gas phase into the state needs to be included to explain the experimental results. We also discuss the stabilization of -N₂ by preadsorbed -N₂, i.e. an attractive interaction between alike molecules but in different bonding configurations.Balzers, ELS Abteilung, FL-9496 Balzers, Fürstentum Liechtenstein     

NO--CO--O2 Reaction on a Metal Catalytic Surface using Eley--Rideal Mechanism

Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal （ER） mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood （LFI） thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.     

Oxygen adsorption on the surface of In2O3 and β-(Ga0.8In0.2)2O3 mixed oxides porous structure

The paper is devoted to the oxygen sensing properties of In_1.2Ga_0.8Se₃ own oxide. The results are compared with theoretical adsorption kinetics. Temperature and time dependences of adsorption mechanisms are discussed.     

Photocatalytic activity enhancement of TiO2 films by micro and nano-structured surface modification

Titanium oxide thin films were deposited by spin coating using a precursor solution of titanium oxide (IV) acetylacetonate. To increase the contact surface area of the films, TiO₂ microspheres were added to the surface of the films. These spheres were 2 μm in diameter and formed agglomerates on the surface. They did not spread uniformly across the substrate, creating different roughnesses and morphologies along the surface of films. Photocatalytic properties of the samples were tested by the degradation of a methyl orange solution. The degradation performance was compared between plain films, films with microspheres and films covered with commercial TiO₂ P25 powder. The results indicate that the samples that were surface modified with TiO₂ microspheres present a photodegradation reaction rate 62 times higher than that obtained for plain TiO₂ films. The rate of reaction of the samples covered with P25 was 2 times greater than that obtained for the samples with microspheres, but the adhesion to the film was better in the case of microspheres. Moreover, samples with microspheres could be reused several times maintaining the same structural and photocatalytic properties.     

Surface enhanced covalency and its effect on the surface states ofd-band metal oxides

The effect of electron-electron interactions on the surface states of ionicd-band oxides is reported. The local density of states of surface cations in the valence band region is significantly increased when surface states occur in the band gap. Coulomb repulsion associated with thissurface enhanced covalency tends to force surface states out of the band gap. These results suggest an explanation of recent experiments on SrTiO₃ and TiO₂.     

EPR and XPS measurements of polymeric catalysts doped with hereopolyacids in oxygen adsorption studies

The goal of our studies was to determine the nature of interactions between catalytic active samples, such as polypyrrole (PPy) doped with: chloride anions, heteropolyacids such as H₅PMo₁₀V₂O₄₀, or H₄SiW₁₂O₄₀, and oxygen particles. In order to reveal the mechanism of the linkage between the catalysts and oxygen we provided the electron paramagnetic resonance (EPR) measurements of synthesized samples in O₂ and N₂ flow. Moreover, the X-ray photoelectron spectroscopy (XPS) measurements were performed to show the properties of doped heteropolyacids and the state of nitrogen in polypyrrole matrix. The results of EPR studies of PPy(Cl), PPy(H₄SiW₁₂O₄₀), PPy(H₅PMo₁₀V₂O₄₀) samples, show that the polypyrrole doped with chloride anions interacts much easier with oxygen than polypyrrole doped with heteropolyacids (in the above given order, of preference with the most active polypyrrole system first). It correlates with XPS results, which show that a molybdenium-vanadium anion is more reduced than a silicon-tungsten one. The redox reactions of heteropolyacids involve the oxidation-reduction of the conjugated polymer chain, leaving no or little place for interactions with oxygen. Polypyrrole doped with H₄SiW₁₂O₄₀ shows some oxygen sensitivity as observed in the EPR studies, as opposed to polypyrrole doped with H₅PMo₁₀V₂O₄₀, which is in line with the XPS results.     

Isotopically selective CVD of silicon by IRMPD of Si2F6

The IRMPD of Si₂F₆ by a CO₂ TEA laser was applied to isotopically selective CVD of silicon. A white film, probably consisting of polymers of SiF₂, was deposited on a metal foil during the irradiation of natural Si₂F₆ with the laser radiation at 951.19 cm^–1 and about 1.5 J cm^–2. Upon heating, the film became dark brown, evolving SiF₄. The³⁰Si content was found to be as high as about 20%.     

Oxygen adsorption on the tungsten (110) plane. Electron impact and thermal desorption at high temperatures

When a layer of oxygen on the (110) plane of tungsten at coverages O/W≦0.5 is heated from 100 K, O⁺ evolution under electron impact becomes almost negligible at 600 K. On further heating, however, a slow, temperature-dependent evolution of O⁺ current is observed atT≳1500 K. For O/W>0.3 there is also desorption under massive bombardment. Once an equilibrium value of O⁺ current has been established, there is rapid adjustment to the appropriate equilibrium value when the temperature changes in the range 1500–1700 K. On cooling toT<1000 K, O⁺ decreases rapidly; on reheating toT>1500 K, O⁺ increases slowly again. Above 1700 K there is thermal desorption which is also reflected in the O⁺ signal. These facts indicate that there is a slow activated evolution of an electron sensitive state above 1500 K, from a reconstructed state formed by heating the low temperature layer toT≧1000 K. The latter state seems to be reformed on cooling below 1500 K.     

TiO2-based superhydrophobic-superhydrophilic patterns: Fabrication via an ink-jet technique and application in offset printing

A superhydrophobic-superhydrophilic pattern was prepared on an anodized Al plate by a new fabrication process. The process consists of five key steps: (1) TiO₂ coating of the plate, (2) surface modification with self-assembled monolayers (SAMs), (3) formation of aqueous UV light-resistant ink patterns by an ink-jet technique, (4) photocatalytic decomposition of SAMs and surface conversion to the superhydrophilic state and (5) removal of the aqueous ink patterns by water washing. It is particularly noteworthy that the wettability pattern can be quickly formed on the plate, without the use of a photomask. The fabricated superhydrophobic-superhydrophilic pattern is shown to be applicable to offset printing.     

Internal energy distribution of recombinatively desorbing D2 from sulfur covered poly-Pd

Rotational and vibrational population distributions have been determined for D₂ molecules recombinatively desorbing from polycrystalline Pd surfaces by tunable vacuum-ultraviolet laser-induced fluorescence. In the temperature range 550 KT _s 1050 K studied in this work a rotational temperature ofT _rot 450 K was found, nearly independent of the surface temperature. Similarly, the vibrational temperature could be described by a value ofT _vib1100 K, being always higher than the surface temperature.     

Effect of Cu adsorption on the tungsten (100) surface resonance

It has recently been observed that adsorbed Au and Hg do not quench the W (100) surface resonance up to monolayer coverage. We report here that Cu does quench the W (100) surface resonance at θ≧0.5 monolayers. This suggests that the effective potential of Cu differs more strongly from that of W than do the effective potentials of Au or Hg.