Coadsorption of oxygen and sodium on Ru(001)

The interaction of oxygen with sodium predosed Ru(001) is studied by means of thermal desorption, Auger and electron loss spectroscopy and work function measurements. The initial sticking coefficient of oxygen is found to increase from 0.45 for bare Ru(001) to 1 for Ru(001) with a 0.35 monolayer sodium coverage. The adsorption capacity of the sodium predosed Ru(001) surface towards oxygen is enhanced from θ_O = 0.5 for clean Ru(001) to θ_O = 1.4 for Ru(001) with a 0.7 monolayer sodium coverage. The work function, electron loss changes and thermal desorption data give evidence that as long as θ_Na is less than 0.25, the oxygen chemisorption phase is characterized mainly by oxygen-Ru bonds and by the absence of strong sodium-oxygen interactions. At high sodium coverages (θ_Na > 0.35), the experimental data indicate the formation of a Na-O compound in the second adsorption layer at high oxygen exposures. When Ru(100) is predosed with sodium (θ_Na ? 0.25), this leads to complete suppression of oxygen penetration into the bulk during heating, the latter process being observed for the oxygen-Ru(001) system.     

The interaction of oxygen with polycrystalldve niobium studied using aes and low-energy sims

The interaction of oxygen with polycrystalline niobium has been studied using both Auger electron spectroscopy and low-energy secondary ion mass spectrometry in the temperature range from 300–1250 K. At higher temperatures there is oxygen dissolution into the bulk but a preferential surface segregation on recooling. Between 300 and 1250 K, there is a rapid initial adsorption into a very stable state which is associated with increases in the Nb⁺ and NbO⁺ yields that are linear with coverage. At 1250 K, further changes are very slow. At 900 K, the initial stage is followed by the adsorption with a lower sticking coefficient (<0.1) as coverage increases from θ = 0.5 to 0.7. This produces an additional larger increase in the yield of Nb⁺ but a much smaller change in NbO⁺. At 300 K, the sticking probability falls more slowly with coverage above θ = 0.5 and the amount of oxygen continues to increase slowly with exposure. The SIMS spectrum shows dramatic increases in Nb⁺, NbO⁺ and NbO⁺₂ yields and the successive appearance of small yields of ions such as Nb₂O⁺₂ and Nb₂O⁺₃ as oxide formation begins. The Nb⁺ yield slowly decreases as further oxidation occurs. Each stage of oxidation has a characteristic secondary ion mass spectrum.     

Adsorption of oxygen on Mo (112) surface precovered with beryllium: formation of overlayer and electronic properties

Adsorption of oxygen on the Mo?(112) surface precovered with a pseudomorphic monolayer of beryllium has been investigated at room temperature by AES, LEED and contact potential difference methods. Such a Be/Mo?(112) substrate is actually a bimetallic surface where closely-packed atomic Mo ridges alternate with rows of Be atoms. It has been found that at small oxygen exposures (Q < 0.3 Langmuir), the initial sticking coefficient for oxygen S _O on Be/Mo?(112) is lower by a factor of ~1/15 than on the clean Mo?(112) surface where S _O is close to unity. However, with increasing the oxygen coverage above θ _O ≈ 0.1, the sticking coefficient showed a nonlinear growth, and oxygen saturation of the surface was achieved at Q = 1.6–1.7 L. Oxygen adsorption decreases the work function of the Be/Mo?(112) surface and gives rise to appearance of some Auger peaks specific to beryllium oxide, which indicates a change in the chemical nature of the surface. The formation of a polar-covalent BeO compound may be responsible for a self-activation of the surface with respect to oxygen which is reflected in the increase of the sticking coefficient observed under growth of oxygen coverage (a kind of autocatalytic reaction). Annealing of the O/Be/Mo?(112) system to T _an  = 1100 K resulted in an additional decrease of the work function and a growth of the ratio between the Auger signals of Be in the oxide and metallic Be adsorbed phases. The presence of BeO molecules was detected up to T _an  = 1600 K, above which they dissociated with desorption of Be.     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Electronic decoupling of surface layers from bulk and its influence in oxidation catalysis: A molecular beam study

Interactions between oxygen and Pd-surfaces have important implications, especially towards oxidation reactions, and influence of subsurface oxygen to oxidation reactions is the focus of the present study. In our efforts to understand the above aspects, CO oxidation reactions have been carried out with mixed molecular beam (MB), consisting CO and O₂, on Pd(1 1 1) surfaces under a wide variety of conditions (T = 400-900 K, CO:O₂ = 7:1 to 1:10). A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd subsurface layers, and its significant influence towards CO oxidation at high temperatures (≥600 K). Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (θ_O-sub), above which the reactive CO adsorption occurs on the surface and simultaneous CO₂ production begins. There is also a significant time delay (Γ) observed between the onset of oxygen adsorption and CO adsorption (and CO₂ production). Above studies suggest an electronic decoupling of oxygen covered surface and subsurface layers, which is slightly oxidized, from the metallic bulk, which induces CO adsorption at high temperatures and simultaneous oxidation to CO₂.     

Temperature dependence of oxidation rate in clean Ge(111)

The temperature dependence of the sticking coefficient of oxygen on a clean Ge(111) surface has been investigated over a wide temperature range from 300 to 1100 °K using three methods. In the interval 300–600 °K a flash technique was used, the desorbed germanium oxide being detected by the time of flight mass-spectrometer. In the range from 500 to 1000 °K the sticking coefficient was measured from the pumping speed of oxygen by the sample surface, and in the range from 800 to 1100 °K the temperature dependence of the etching speed by oxygen was determined.The measured temperature dependence of the sticking coefficient is complex. It increases between 300 and 400 °K, remaining virtually constant from 400 to 500 °K with a new increase in the range from 500 to 1000 °K. A rapid fall in the sticking coefficient was observed at temperatures above 1000 °K.The dependence of the adsorption coverage on exposure has also been obtained for sample temperatures of 300, 350, 400 and 500 and 600 °K. The form of the adsorption curves differs considerably from a theoretical one based on a decrease in the sticking coefficient with coverage given by s = s₀(1 ? θ)². At 600 °K the sticking coefficient decreases more slowly than predicted by this equation. On the contrary, at 300 °K it begins to decrease rapidly at low coverages less than 0.1 of a monolayer.To explain the results it is assumed that oxygen molecules adsorb on the surface structural defects. At 300 °K such defects may be in the form of steps or other morphological disturbances on the surface, and above 500 °K they are probably equilibrium thermal defects, for example, surface vacancies.     

Interaction of H2O with a clean and oxygen precovered Ni(110) surface studied by XPS

The adsorption and reaction of H₂O on clean and oxygen precovered Ni(110) surfaces was studied by XPS from 100 to 520 K. At low temperature (T<150 K), a multilayer adsorption of H₂O on the clean surface with nearly constant sticking coefficient was observed. The O 1s binding energy shifted with coverage from 533.5 to 534.4 eV. H₂O adsorption on an oxygen precovered Ni(110) surface in the temperature range from 150 to 300 K leads to an O 1s double peak with maxima at 531.0 and 532.6 eV for T=150 K (530.8 and 532.8 eV at 300 K), proposed to be due to hydrogen bonded O_ads… HOH species on the surface. For T>350 K, only one sharp peak at 530.0 eV binding energy was detected, due to a dissociation of H₂O into O_ads and H₂. The s-shaped O 1s intensity-exposure curves are discussed on the basis of an autocatalytic process with a temperature dependent precursor state.     

On the kinetics of oxygen adsorption on a Pt(111) surface

The kinetics of O₂ adsorption on a clean Pt(111) surface were investigated in the temperature range 214–400°C. The oxygen coverage was measured by CO titration as well as Auger electron spectroscopy both of which show the same dependence on O₂ exposure. The initial sticking coefficient on clean Pt(111) is 0.08–0.10 and decreases exponentially with increasing oxygen coverage. For θ > 0.23 a (2 × 2)-O LEED pattern was observed. The highest oxygen coverage obtained was approximately 0.45. A theoretical model was proposed which correlates the coverage dependence of the sticking coefficient with adsorbate interactions in the chemisorbed state. These interactions cause a coverage dependent activation energy of adsorption assuming the existence of a precursor state. Experiments dealing with the effect of carbon contamination on the sticking coefficient showed that the initial sticking coefficient decreases with increasing carbon coverage.     

Basic studies of the oxygen chemistry of silver: Oxygen,dioxygen and superoxide on potassium-dosed Ag(100)

The adsorption—desorption and structural properties of oxygen phases on K-dosed Ag(100) have been investigated. At 298 K, potassium enhances the sticking probability of O₂ on Ag(100) by a factor of ?100; the initial sticking probability and saturation uptake of O₂ are proportional to the potassium coverage (θ_K) for θ_K < 0.5. For θ_K < 0.5 the desorption spectra reveal the presence of three distinct oxygen species — O(a), O₂(a) and dissolved O. The dioxygen species, O₂(a), is associated with the presence of subsurface K and its identity is confirmed by isotope-mixing experiments and CO titration. For θ_K > 1.0 LEED shows the formation of two ordered structures and two additional features appear in the O₂ desorption spectra. One of these structures is ascribed to the growth of (001) oriented potassium superoxide (KO₂). The oxygen chemistry of Na and Rb-dosed Ag surfaces is compared with the results of the present work.     

Adsorption of oxygen and oxidation of CO on the ruthenium (001) surface

The adsorption of oxygen on the ruthenium (001) surface has been studied using a combination of techniques: LEED/Auger, Kelvin probe contact potential changes, and flash desorption mass spectrometry. Oxygen is rapidly adsorbed at 300 K, forming an ordered LEED structure having apparent (2 × 2) symmetry. Two binding states of oxygen are inferred from the abrupt change in surface work function as a function of oxygen coverage. LEED intensity measurements indicate that the oxygen layer undergoes an order-disorder transition at temperatures several hundred degrees below the onset of desorption. The order-disorder transition temperature is a function of the oxygen coverage, consistent with two binding states. A model involving the adsorption of atomic oxygen at θ < 0.5 and the formation of complexes with higher oxygen content at θ > 0.5 is proposed. The oxidation of CO to form CO₂ was found to have the maximum rate of production at a ruthenium temperature of 950 K.     

Oxygen adsorption on an alkali metal-covered Ni(100) surface

The oxygen chemisorption on an alkali (Na, K, Cs) covered Ni(100) surface and its initial oxidation were studied by Auger and electron energy loss spectroscopy (ELS). It was found that in the presence of an alkali metal, the sticking coefficient S remains unity up to a given oxygen coverage of θ_O^cwhose value depends on the alkali overlayer concentration and the ionicity of the Ni-alkali metal bond. At a given oxygen coverage, the line shapes of Auger and loss spectra are almost the same for alkali-covered and clean Ni(100), which suggests that alkali metals cause no change in the character of the Ni-O bond. The effect of alkali metals is associated with increasing electron charge in the surface region, which facilitates oxygen chemisorption. The enhanced surface oxygen concentration in the presence of an alkali metal results in the formation of an oxide phase at lower oxygen exposures than is the case of clean Ni surfaces.     

Molecular binding states on clean and oxidized surfaces: SiO(g) + W(clean) and SiO(g) + W(oxidized)

The interactions between a molecular beam of SiO(g) and a clean and an oxidized tungsten surface were examined in the surface temperature range 600 to 1700 K by mass spectrometrically determined sticking probabilities, by flash desorption mass spectrometry (FDMS) and by Auger electron spectroscopy (AES). The sticking probability, S, of SiO has been determined as a function of coverage and of surface temperature for the clean and the oxidized tungsten surface. Over the temperature range studied and at zero coverage S = 1.0 and 0.88 for the clean and oxidized tungsten surfaces respectively. The results are consistent with both FDMS and AES. For coverage up to one monolayer there is one major adsorption state of SiO on the clean tungsten surface. FDMS shows that T_m = constant (T_m is the surface temperature at which the desorption rate is maximum) and that desorption from this state is described by a simple first order desorption process with activation energy, E_d = 85.3 kcal mole^?1 and pre-exponential factor, ν = 2.1 × 10¹⁴ sec^?1. AES shows that the 92 eV peak characteristic of silicon dominates. In contrast on the oxidized tungsten surface, T_m shifts to higher temperatures with increasing coverage. The data indicate a first order desorption process with a coverage dependent activation energy. At low coverage (θ ? 0.14) there is an adsorption state with E_d = 120 kcal mole^?1 and ν = 7.6 × 10¹⁹, while at θ = 1.0, E_d = 141 kcal mole^?1. This variation is interpreted as due to complex formation on the surface. AES shows that on oxidized tungsten, in contrast to clean tungsten, the dominant peaks occur at 64 and 78 eV, and these peaks are characteristic of higher oxidation states of silicon. Thus, it is concluded that SiO exists in different binding states on clean and oxidized tungsten surfaces.     

A molecular beam study of the adsorption and desorption of oxygen from a Pt(111) surface

The adsorption and desorption of O₂ on a Pt(111) surface have been studied using molecular beam/surface scattering techniques, in combination with AES and LEED for surface characterization. Dissociative adsorption occurs with an initial sticking probability which decreases from 0.06 at 300 K to 0.025 at 600 K. These results indicate that adsorption occurs through a weakly-held state, which is also supported by a diffuse fraction seen in the angular distribution of scattered O₂ flux. Predominately specular scattering, however, indicates that failure to stick is largely related to failure to accommodate in the molecular adsorption state. Thermal desorption results can be fit by a desorption rate constant with pre-exponential ν_d = 2.4 × 10^?2 cm² s^?1 and activation energy E_D which decreases from 51 to 42 kcal/mole^?1 with increasing coverage. A forward peaking of the angular distribution of desorbing O₂ flux suggests that part of the adsorbed oxygen atoms combine and are ejected from the surface without fully accomodating in the molecular adsorption state. A slight dependance of the dissociative sticking probability upon the angle of beam incidence further supports this contention.     

Adsorption isotherms of oxygen on tungsten (100), (110) and (111) surfaces in the pressure range 10−9 to 10−4 torr and temperature range 1500 to 2600 k,as measured by AES

This paper is a continuation of a previous investigation of oxygen adsorption on tungsten at high temperature using Auger electron spectroscopy. In this paper the adsorption isotherms of oxygen on (100), (110) and (111) faces of tungsten are reported. It is shown that these isotherms can be described by an equation of the form pO₂ = AF(θ) exp [?q(θ)/ kT]. The coverage depended functions F(θ) and q(θ) evaluated from the isotherms are different for all three investigated faces. The isosteric adsorption energy q has following initial values at very low oxygen coverage: q₁₀₀ = 6.1 eV, q₁₁₀ = 6.8 eV and q₁₁₁ = 6.5 eV. Increasing the oxygen coverage has only small influence on q₁₁₁; it changes from the initial value to q₁₁₁ ≈ 6.0 eV at θ ≈ 0.3 and remains constant at this value up to θ ≈ 1. q₁₁₀ shows the strongest dependence on oxygen coverage. It decreases rapidly at low coverages, slowly at moderate coverages and reaches the value q₁₁₀ = 5.0 atθ ≈ 1. The variation of q₁₁₀ with increasing oxygen coverage is monotonie from the initial value to q₁₁₁ = 4.9 eV at θ ≈ 1. Assuming that the atomic oxygen is the dominant species leaving the tungsten surface at high temperatures the functions F(θ) are used to calculate the oxygen equilibration probability ζO₂ (high temperature sticking probability) as a function of oxygen coverage θ. The main characteristic of ζO₂(θ) for all three faces is that it shows a maximum for (100) and (111) faces at θ = 0.3 and for (110) face at θ = 0.55.     

The co-adsorption of copper and oxygen on a tungsten {100} surface

The co-adsorption of Cu on O₂ and a W{100}surface is studied by Auger electron spectroscopy (AES), thermal desorption (TD), low energy electron diffraction (LEED) and by work function change (δø) measurements. It is shown that the presence of Cu on the surface initially decreases s_O, the sticking coefficient of O₂. For longer oxygen exposures and for higher adsorption temperatures, θ_O reaches values larger than those on the clean surface for the same O₂ exposure. Except at the highest θ_O values and temperatures, the sticcking coefficient for copper, s_Cu, is unity and is independent of the oxygen coverage θ_O in the range studied (0 ? θ_O ? 2). Co-adsorption at room temperatures does not produce any long range order while co-adsorption at elevated temperature leads to the ordered structures (1 × 1), p(2 × 1), p(2 × 2) and c(2 × 2). The saturation coverage of the two dimensional co-adsorbate at 800 K is given by the relation $\text{θ}{}_{\mathrm{Cu}}\text{+}\text{8}\text{5}\text{θ}{}_{\mathrm{O}}\text{= 2}$. The work function is a complicated function of θ_O and θ_Cu and is determined predominantly by the temperature at which oxygen is adsorbed. At high temperatures the sequence of adsorption has no influence, in contrast to the room temperature behavior.     

Adsorption of oxygen on a Cu{110} surface with and without the influence of A keV Ne+ beam: Stage I: Coverages up to half a monolayer

Low Energy Ion Scattering has been used to study the interaction of molecular oxygen with a Cu{110} surface. The amount of adsorbed atomic oxygen was monitored by the 4 keV Ne⁺¦O reflection signal. In the first adsorption stage (coverage less than half a monolayer) the sticking probability varied proportional to the number of empty adsorption sites: S = S₀ (1 ? $\text{}\text{?}$gq). It turned out not to be influenced by the Ne⁺ bombardment. The initial sticking probability S₀ was found to be ≈ 0.24. In this first adsorption stage the oxygen-covered surface is reconstructed according to the “missing row” model, leading to a (2 × 1) LEED pattern.     

Ordered oxygen overlayers on Cr(100) observed by leed and photoemission

Chemisorbed oxygen atoms on Cr(100) induce strong O(2p) derived surface resonances which are studied by angle resolved photoemission. Well ordered structures are observed after annealing (300°C). In the submonolayer range (θ_O < 1) a study of the symmetry and dispersion of the O(2p) derived features shows the two-dimensional Bloch character associated with either a c(2 × 2)-O surface at low coverages (θ_O?0.25) or a (1 × 1)-O structure at high coverages (θ_O?0.9). When combined with LEED observations and work function data this study indicates that both structures coexist around θ_O = 0.5 and chemisorbed oxygen is probably incorporated into the fourfold hollow sites. At θ_O > 1, the onset of oxidation is clearly shown in the valence band and core level spectra and the data support the existence of a thin spinel-like oxide layer.     

A LEED-AES study of the initial stages of oxidation of Fe (001)

LEED and AES have been used to study the structural changes and kinetics of the initial interaction between Fe(001) and oxygen at room temperature. The AES oxygen signal was quantified by using a two-dimensional oxide layer as a calibration point. This reproducible oxide layer was prepared by the high temperature reaction of H₂O at 10^?6 torr with Fe(001). The initial oxygen sticking coefficient was observed to be close to unity, which suggests that the chemisorption is non-activated and involves a mobile adsorption step. The rate of chemisorption decreased as (1-Θ) and exhibited a minimum at Θ = 0.5. LEED data indicate that the minimum value of the sticking coefficient corresponded to the completion of a c (2 × 2) surface structure. Upon additional exposure to oxygen, an increase in the sticking coefficient was observed in conjunction with the disappearance of the c (2 × 2) and a gradual fade out of all diffraction features. After mild heating, epitaxial FeO (001) and FeO (111) structures were observed. The simultaneous appearance of a shifted M_2,3M_4,5M_4,5 iron Auger transition with the increase in the sticking coefficient and the disappearance of the c (2 × 2) indicated that oxide nucleated on the surface after the complete formation of the c (2 × 2) structure. The relatively high sticking coefficient during the initial oxidation indicates that formation of a mobile adsorbed oxygen state precedes the formation of oxide.     

Interaction de l'oxygène aux basses pressions avec la solution solide niobium-oxygène à haute température: I. Èquilibre de segrégation — chimisorption

Interactions between oxygen under low pressure and a niobium-oxygen solid solution had been studied, in the regime where adsorption is the rate-determining step, from 1000 to 1700 K. It is shown that at saturation of solid solution, there exists a constant limiting value Θ_l of superficial coverage, comparable to a limiting bulk concentration c_l. The ratios θ = Θ/Θ_l and ? = c/c_l are called “relative ratio of occupation” (superficial and bulk). $\text{K}$_SV is the equilibrium constant of segregation between adsorbed and dissolved oxygen atoms: (O_diss^?v) + σ ? (O_chim?σ) + v (σ and v being respectively surface and bulk sites), $\text{K}$_SV = [(1 ? θ)/θ] [?/(1 ? ?)]. The experimentally determined expression: $\text{K}$_SV = 5.7 exp[?(22.1 ? 12.1 θ)/ RT] shows that lateral superficial interactions have a large influence on the enthalpy of transfer between the bulk and the surface of the sample. Adsorption is direct and non activated. At the solubility limit, only a fraction of the superficial sites is occupied. We estimate it to be one half. The sticking probability b of oxygen on a niobium oxygen solid solution is given by b = (1 ? θ/2)², its value at zero coverage being estimated as unity.     

Chemisorption of CO on the unreconstructed Pt(100) surface

The chemisorption of CO on the clean, unreconstructed Pt(100)-1 × 1 surface was investigated by LEED and XPS. Three LEED patterns, c(2 × 2), (√2 × 3√2) R45° and c(4 × 2), were observed with increasing CO exposure and structure models corresponding to these LEED patterns were proposed. The absolute coverage of CO was determined by combining the O(1s) XPS data with coverage information derived from LEED. The maximum CO coverage thus obtained was θ = 0.75 and the initial sticking coefficient was determined to be s₀ = 0.6. This coverage calibration can also be utilized for other oxygen containing molecules by comparing the corresponding O(1s)it peak intensities.