Adsorption and solution of H2, D2, N2, O2 and CO by (100) Ta

Sticking coefficients, saturation densities, and solution rates of gases on (100) Ta are obtained by comparing with results on (100) W using Auger electron spectroscopy and flash desorption. Hydrogen has a lower sticking coefficient on (100) Ta than on polycrystalline Ta, but solution occurs readily even at 78°K. Differences between H₂ and D₂ are observed for both adsorption and solution. Nitrogen is confined to the surface of Ta for T < ≈500°K, and adsorbed nitrogen dissolves with an activation energy of ≈2.5 kcal mole^?1 upon heating to higher temperatures. The saturation density of O₂ at 300° K is approximately twice that on (100) W. The first monolayer dissolves at ≈500°K but the second dissolves or desorbs only at much higher temperatures. Carbon monoxide adsorbs without solution of either species at 300°K. At ≈500°K carbon dissolves completely leaving oxygen which desorbs at much higher temperature.     

Visible light induced photodesorption of NO from the α-Cr2O3(0001) surface

Nitric oxide chemistry and photochemistry on the Cr-terminated surface of α-Cr₂O₃(0001) were examined using temperature programmed desorption (TPD), sticking coefficient measurements and photodesorption. NO exposed to α-Cr₂O₃(0001) at 100 K binds at surface Cr cation sites forming a strongly bound surface species that thermally desorbs at 320–340 K, depending on coverage. No thermal decomposition was detected in TPD in agreement with previous results in the literature. Sticking probability measurements at 100 K indicated near unity sticking for NO up to coverages of ~ 1.3 ML, with additional adsorption with higher exposures at decreased sticking probability. These results suggest that some Cr cation sites on the α-Cr₂O₃(0001) surface were capable of binding more than one NO molecule, although it is unclear whether this was as separate NO molecules or as dimers. Photodesorption of adsorbed NO was examined for surface coverages below the 1 ML point. Both visible and UV light were shown to photodesorb NO without detectable NO photodecomposition. Visible light photodesorption of NO occurred with a greater cross section than estimated using UV light. The visible light photodesorption event was not associated with bandgap excitation in α-Cr₂O₃(0001), but instead was linked to excitation of a surface Cr^3 +–NO^? charge transfer complex. These results illustrate that localized photoabsorption events at surface sites with unique optical properties (relative to the bulk) can result in unexpected surface photochemistry.     

Nitric oxide chemisorption on Re(0001) at 100 and 300 K: Evolution of the adsorbed layer during annealing from 100 to 700 K; XPS,UPS, TDS and work function measurements

At 100 K NO is molecularly adsorbed on Re(0001). Bridge bonded and linear species have been identified by XPS and UPS measurements. Moreover a weakly bonded species reversibly adsorbed at 100 K has been found, but not precisely identified. As the temperature of the surface is increased a complex transformation of the layer occurs: the weakly bonded molecules are probably transformed into a more strongly bonded state and desorb between 100 and 300 K. One part of the linear species desorbs between 300 and 500 K giving the α₂ molecular state, the other part dissociates and desorbs between 600 and 700 K giving the β₁ nitrogen molecules. In the same temperature range the bridge bonded molecules dissociate into nitrogen and oxygen atoms, but nitrogen desorbs into the gas phase between 700 and 1100 K as β₂ and β₃ states with a second order process. Oxygen is adsorbed as atoms and desorbs at higher temperature. If adsorption takes place at room temperature, NO is mainly dissociated and nitrogen desorbs as β₂ and β₃ states with a second order process.     

Adsorption-desorption properties,coadsorption, and surface structural chemistry of chlorine and oxygen on Ag(331)

At 300 K oxygen chemisorbs on Ag(331) with a low sticking probability, and the surface eventually facets to form a (110)?(2 × 1) O structure with ΔΦ = +0.7 eV. This facetting is completely reversible upon O₂ desorption at ~570 K. The electron impact properties of the adlayer, together with the LEED and desorption data, suggest that the transition from the (110) facetted surface to the (331) surface occurs at an oxygen coverage of about two-thirds the saturation value. Chemisorbed oxygen reacts rapidly with gaseous CO at 300 K, the reaction probability per impinging CO molecule being ~0.1. At 300 K chlorine adsorbs via a mobile precursor state and with a sticking probability of unity. The surface saturates to form a (6 × 1) structure with ΔΦ = +1.6 eV. This is interpreted in terms of a buckled close-packed layer of Cl atoms whose interatomic spacing is similar to those for Cl overlayers on Ag(111) and Ag(100). Desorption occurs exclusively as Cl atoms with E_d ~ 213 kJ mol^?1; a comparison of the Auger, ΔΦ, and desorption data suggests that the Cl adlayer undergoes significant depolarisation at high coverages. The interaction of chlorine with the oxygen predosed surface, and the converse oxygen-chlorine reaction are examined.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

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.     

Chemisorption of H2 on W(100): Absolute sticking probability,coverage, and electron stimulated desorption

Measurements of both the absolute sticking probability near normal incidence and the coverage of H₂ adsorbed on W(100) at ~ 300K have been made using a precision gas dosing system; a known fraction of the molecules entering the vacuum chamber struck the sample crystal before reaching a mass spectrometer detector. The initial sticking probability S₀ for H₂/W(100) is 0.51 ± 0.03; the hydrogen coverage extrapolated to S = 0 is 2.0 × 10¹⁵ atoms cm^?2. The initial sticking probability S₀ for D₂/W(100) is 0.57 ± 0.03; the isotope effect for sticking probability is smaller than previously reported. Electron stimulated desorption (ESD) studies reveal that the low coverage β₂ hydrogen state on W(100) yields H⁺ ions upon bombardment by 100 eV electrons; the ion desorption cross section is ~ 1.8 × 10^?23 cm². The H⁺ ion cross section at saturation hydrogen coverage when the β₁ state is fully populated is ? 10^?25 cm². An isotope effect in electron stimulated desorption of H⁺ and D⁺ has been found. The H⁺ ion yield is ? 100 × greater than the D⁺ ion yield, in agreement with theory.     

Chemisorption and surface reactivity of nitric oxide on clean and sodium-dosed Ag(110)

The chemisorption of NO on clean and Na-dosed Ag(110) has been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption into the α-state occurs at 300 K with an initial sticking probability of ～0.1, and the surface is saturated at a coverage of about $\text{1}\text{25}$. Desorption occurs without decomposition, and is characterised by an enthalpy of E_d ～104 kJ mol^?1 — comparable with that for NO desorption from transition metals. Surface defects do not seem to play a significant role in the chemistry of NO on clean Ag, and the presence of surface Na inhibits the adsorption of αNO. However, in the presence of both surface and subsurface Na, both the strength and the extent of NO adsorption are markedly increased and a new state (β₁NO) with E_d ～121 kJ mol^?1 appears. Adsorption into this state occurs with destruction of the Ag(110)-(1 × 2)Na ordered phase. Desorption of β₁NO occurs with significant decomposition, N₂ and N₂O are observed as geseous products, and the system's behaviour towards NO resembles that of a transition metal. Incorporation of subsurface oxygen in addition to subsurface Na increases the desorption enthalpy (β₂NO), maximum coverage, and surface reactivity of NO still further: only about half the adsorbed layer desorbs without decomposition. The bonding of NO to Ag is discussed, and comparisons are made with the properties of α and βNO on Pt(110).     

The adsorption of chlorine and chloridation of Ag(111)

The adsorption of chlorine on the Ag(111) surface has been studied using LEED, Auger and temperature programmed desorption. Chlorine adsorbs dissociately with an initial sticking probability of ~ 0.4, and a precursor state is implicated in the chemisorption process. The chlorine appears to form a close-packed monolayer with the same packing density as in AgCl(111), and is epitaxially related to the substrate mesh. Chlorine continues to adsorb above a monolayer in coverage, though the sticking probability drops precipitately, being ~ 0.01 after the adsorption of 5 monolayers at 300 K. There is little increase in the chlorine Auger signal above one monolayer coverage at 300 K, but when adsorption is carried out at 240 K the chlorine signal is more than doubled. This is interpreted as being due to the formation of a layer structure of alternate Cl and Ag layers at the lower temperature, while adsorption at 300 K results in dissolution of subsurface Cl into the bulk of the crystal. Upon heating, the low temperature layer structure is destroyed, the chlorine signal diminishes to a limiting value at 450 K equivalent to the value for one adsorbed monolayer — apparently due to the dissolution of the near surface Cl layers into the bulk. However, the chlorine re-emerges at the surface at ~ 600 K, probably due to an exothermic heat of solution of Cl in the silver lattice. Desorption from the multilayers peaks at 670 K and both AgCl and Ag are desorbed coincidently with kinetics identical to those for the sublimation of bulk AgCl (ΔH = 235 kJ mol^?1, ΔS = 90 JK^?1 mol^?1). After the multilayers have desorbed, the final Cl layer desorbs in a higher temperature peak ( ~ 760 K) as AgCl (no silver desorption) which shows complex desorption kinetics indicative of the strong influence of a precursor state in the desorption process.     

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.     

An Auger spectroscopic study of the kinetic behavior of adsorbed oxygen on palladium

The adsorption of oxygen on polycrystalline palladium, the kinetics of the reaction of adsorbed oxygen with carbon monoxide and the amount of adsorbed oxygen present during the catalyzed reaction, $\text{CO +}\text{1}\text{2}\text{O}{}_2\text{→ CO}{}_2$, were studied by Auger electron spectroscopy. At temperatures below 783 K, the initial sticking probability is high (~0.8). Adsorbed oxygen and CO react with high probability and low activation energy to form carbon dioxide. The reaction is first order with respect to carbon monoxide pressure and zero order in oxygen coverage. Oxygen coverages measured during the CO-oxidation reaction decrease sharply around P_CO ? P_O2 and are very small when P_CO >P_O2. The reaction kinetics are discussed using a modified Eley-Rideal mechanism involving strongly adsorbed oxygen atoms and surface carbon monoxide in a short-lived state. The oxygen adsorption phenomena are correlated with the reaction kinetics.     

Adsorption of oxygen on Pt(111)

Oxygen adsorbed on Pt(111) has been studied by means of temperature programmed thermal desorption spectroscopy (TPDS). high resolution electron energy loss spectroscopy (EELS) and LEED. At about 100 K oxygen is found to be adsorbed in a molecular form with the axis of the molecule parallel to the surface as a peroxo-like species, that is, the OO bond order is about 1. At saturation coverage (θ_mol= 0.44) a $\text{(}\text{3}\text{2}\text{×}\text{3}\text{2}\text{)R15°}$ diffraction pattern is observed. The sticking probability S at 100 K as a function of coverage passes through a maximum at θ = 0.11 with S = 0.68. The shape of the coverage dependence is characteristic for adsorption in islands. Two coexisting types of adsorbed oxygen molecules with different OO stretching vibrations are distinguished. At higher coverages units with v-OO = 875 cm^?1 are dominant. With decreasing oxygen coverages the concentration of a type with v-OO = 700 cm^?1 is increased. The dissociation energy of the OO bond in the speices with v-OO = 875 cm^?1 is estimated from the frequency shift of the first overtone to be ~ 0.5 eV. When the sample is annealed oxygen partially desorbs at ~ 160K, partially dissociates and orders into a p(2×2) overlayer. Below saturation coverage of molecular oxygen, dissociation takes place already at92 K. Atomically adsorbed oxygen occupies threefold hollow sites, with a fundamental stretching frequency of 480 cm^?1. In the non-fundamental spectrum of atomic oxygen the overtone of the E-type vibration is observed, which is “dipole forbidden” as a fundamental in EELS.     

Coadsorption of NO and other small gases (H2 and CO) on polycrystalline rhodium surface

The coadsorption of NO and other small gases (H₂ and CO) on a polycrystalline Rh filament has been studied by thermal desorption mass spectroscopy, using ¹⁵NO. The sample was exposed to a mixture of nitric oxide and other gases with various concentrations of ¹⁵NO at room temperature. It is indicated that NO, CO and H₂ coadsorbs on the rhodium surface, and NO desorbs as N₂ and O₂. NO is adsorbed mainly in the dissociation at lower coverage and molecular adsorption becomes dominant at higher coverage. But the amount of desorbed O₂ was very small. The chemisorption of CO is affected by the chemisorbed NO. Thermal desorption of hydrogen is detected when the value of P_15NO/P_CO is very small. The hydrogen adsorbed on the rhodium surface is replaced by NO with a longer exposure time.     

Adsorption and desorption of ammonia,hydrogen, and nitrogen on ruthenium (0001)

The adsorption of ammonia, hydrogen, and nitrogen on a Ru(0001) surface have been investigated by Auger electron spectroscopy, low-energy electron diffraction, and thermal flash desorption. The adsorption of ammonia on Ru(0001) can be divided into a low temperature mode (100 K) and a higher temperature mode (300–500 K). For a crystal temperature of 100 K the ammonia adsorbs into two weakly bound molecular γ states with s = 0.2. The ammonia desorbs as NH₃ molecules with desorption energies of 0.32 and 0.46 eV. At 300–500 K adsorption occurs via an activated process with a low sticking probability (s ? 2 × 10^?4).This adsorption is accompanied by dissociation and formation of an apparent (2 × 2) LEED pattern. Hydrogen adsorbs readily (s = 0.4) on Ru(0001) at 100 K and desorbs with 2nd order kinetics in the temperature range 350–450 K. Nitrogen does not appreciably adsorb on Ru(0001) even at 100 K; maximum nitrogen coverage obtained was estimated to be <2% of a monolayer. Changes in the ammonia flash desorption spectra after hydrogen preadsorption at 100 K will be discussed.     

Cyanide chemistry of rubidium-dosed silver and the use of cyanogen as a titrant for surface alkali

The presence of adsorbed rubidium induces dissociation of cyanogen during chemisorption and leads to a mixed adiayer containing two kinds of cyanide surface species. One of these is weakly bound in an undissociated state and desorbs as (CN)₂ (E_d ? 100 k J mole^?1). A second species is the result of dissociation to CN_adsand appears to be closely associated with the Rb adatoms. This species desorbs exclusively as RbCN (E_d ~ 165 kJ mole^?1) with a kinetic order of between zero and unity depending on the surface coverage. This behaviour, together with the electron impact properties of the Rb + CN overlayer suggest that nucleation and island growth of RbCN occurs above a certain critical coverage. This model can account for the way in which the initially large ESD cross-section for CN loss (~3.5 × 10^?18 cm²) rapidly decreases towards zero with decreasing coverage. It is demonstrated that the special properties of the Ag-(CN)₂-Rb system permit (CN)₂ to be used as a specific titrant for surface alkali, and the technique is used to obtain a value for the activation energy (30 kJ mole^?1) for surface → bulk diffusion of Rb in Ag, as well as the above cross-section to ESD.     

Chemisorption of nitrogen on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-absorption infrared spectroscopy has been combined with thermal desorption and surface coverage measurements to study nitrogen adsorption on a {111}-oriented platinum ribbon under ultrahigh vacuum conditions. Desorption spectra show a single peak (at 180 K) after adsorption at 120 K, giving a coverage-independent activation energy for desorption'of ～40 kJmol^?1. The initial sticking probability at this temperature is 0.15, and the maximum uptake was ～1.1 × 10¹⁴ molecule cm^?2. The adsorbed nitrogen was readily displaced by CO, h₂ and O₂. An infrared absorption band was observed with a peak located at 2238 ± 1 cm^?1, and a halfwidth of 9 cm^?1, with a molecular intensity comparable to that reported for CO on Pt{111}. The results are compared with data for chemisorption on other group VIII metals. An earlier assignment of infrared active nitrogen to B₅ sites on these metals is brought into question by the present results.     

The adsorption of CO,O2, and H2 on Pt(100)-(5×20)

The adsorption/desorption characteristics of CO, O₂, and H₂ on the Pt(100)-(5 × 20) surface were examined using flash desorption spectroscopy. Subsequent to adsorption at 300 K, CO desorbed from the (5×20) surface in three peaks with binding energies of 28, 31.6 and 33 kcal gmol^?1. These states formed differently from those following adsorption on the Pt(100)-(1 × 1) surface, suggesting structural effects on adsorption. Oxygen could be readily adsorbed on the (5×20) surface at temperatures above 500 K and high O₂ fluxes up to coverages of $\text{2}\text{3}$ of a monolayer with a net sticking probability to ssaturation of ? 10^?3. Oxygen adsorption reconstructed the (5 × 20) surface, and several ordered LEED patterns were observed. Upon heating, oxygen desorbed from the surface in two peaks at 676 and 709 K; the lower temperature peak exhibited atrractive lateral interactions evidenced by autocatalytic desorption kinetics. Hydrogen was also found to reconstruct the (5 × 20) surface to the (1 × 1) structure, provided adsorption was performed at 200 K. For all three species, CO, O₂, and H₂, the surface returned to the (5 × 20) structure only after the adsorbates were completely desorbed from the surface.     

Adsorption of sulfur dioxide and the interaction of coadsorbed oxygen and sulfur on Pt(111)

The adsorption of sulfur dioxide and the interaction of adsorbed oxygen and sulfur on Pt(111) have been studied using flash desorption mass spectrometry and LEED. The reactivity of adsorbed sulfur towards oxygen depends strongly on the sulfur surface concentration. At a sulfur concentration of 5 × 10¹⁴ S atoms cm^?2 ($\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ structure) oxygen exposures of 5 × 10^?5 Torr s do not result in the adsorption of oxygen nor in the formation of SO₂. At concentrations lower than 3.8 × 10¹⁴ S stoms cm^?2 ((2 × 2) structure) the thermal desorption following oxygen dosing at 320 K yields SO₂ and O₂. With decreasing sulfur concentration the amount of desorbing O₂ increases and that of SO₂ passes a maximum. This indicates that sulfur free surface regions, i.e. holes or defects in the (2 × 2) S structure, are required for the adsorption of oxygen and for the reaction of adsorbed sulfur with oxygen. SO₂ is adsorbed with high sticking probability and can be desorbed nearly completely as SO₂ with desorption maxima occurring at 400, 480 and 580 K. The adsorbed SO₂ is highly sensitive to hydrogen. Small H₂ doses remove most of the oxygen and leave adsorbed sulfur on the surface. After adsorption of SO₂ on an oxygen predosed surface small amounts of SO₃ were desorbed in addition to SO₂ and O₂ during heating. Preadsorbed oxygen produces variations of the SO₂ peak intensities which indicate stabilization of an adsorbed species by coadsorbed oxygen.     

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.