Adsorption of carbon monoxide,oxygen, hydrogen,nitrogen, ethylene and benzene on an iridium (110) surface; Correlation with other iridium crystal faces

The interaction of CO, O₂, H₂, N₂, C₂H₄ and C₆H₆ with an Ir(110) surface has been studied using LEED, Auger electron spectroscopy and flash desorption mass spectroscopy. Adsorption of oxygen at 30°C produces a (1× 2) structure, while a c(2 × 2) structure is formed at 400°C. Two peaks have been detected in the thermal desorption spectrum of oxygen following adsorption at 30°C. The heat of adsorption of hydrogen is slightly higher on Ir(110) than on Ir(111). Adsorption of carbon monoxide at 30°C produces a (2 × 1) surface structure. The main CO desorption peak is found around 230, while two other desorption peaks are observed around 340 and 160°C. At exposures between 250 and 500°C carbon monoxide adsorption yields a c(2 × 2) structure and a desorption peak around 600°C. Carbon monoxide is adsorbed on an Ir(110) surface partly covered with oxygen or carbon in a new binding state with a significantly higher desorption temperature than on the clean surface. Adsorption of nitrogen could not be detected on either clean or on carbon covered Ir(110) surfaces. The hydrocarbon molecules do not form ordered surface structures on Ir(110). The thermal desorption spectra obtained after adsorption of C₆H₆ or C₂H₄ are similar to those reported previously for Ir(111) consisting mostly of hydrogen. Heating the (110) surface above 700°C in the presence of C₆H₆ or C₂H₄ results in the formation of an ordered carbonaceous overlayer with (1 × 1) structure. The results are compared with those obtained previously on the Ir(111) and Ir(755) or stepped [6(111) × (100)] surfaces. The CO adsorption results are discussed in relation to data on similar surfaces of other Group VIII metals.     

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.     

Adsorption of hydrogen on a Pt(111) surface

The H₂/Pt(111) system has been studied with LEED, ELS, thermal desorption spectroscopy and contact potential measurements. At 150 K H₂ was found to adsorb with an initial sticking coefficient of about 0.1, yielding an atomic H:Pt ratio of about 0.8:1 at saturation. H₂/D₂ exchange experiments gave evidence that adsorption is completely dissociative. No exrea LEED spots due to adsorbed hydrogen were observed, but the adsorbate was found to strongly damp the secondary Bragg maxima in the I/V spectrum of the specular beam. The primary Bragg maxima were slightly increased in intensity and shifted to somewhat lower energy. A new characteristic electron energy loss at ?15.4 eV was recorded upon hydrogen adsorption. The thermal desorption spectra were characterized by a high temperature (β₂-) state desorbing with second order kinetics below 400 K and a low temperature (β₂-) state that fills up, in the main, after the first peak saturates. The β₂-state is associated with an activation energy for desorption E1 of 9.5 kcal/mole. The decrease E1 with increasing coverage and the formation of the β₁-state are interpreted in terms of a lateral interaction model. The anomalous structure in the thermal desorption spectra is attributed to domains of non-equilibrium configuration. The work function change Δ? was found to have a small positive maximum (～ 2 mV) at very low hydrogen doses (attributed to structural imperfections) and then to decrease continuously to a value of ?230 mV at saturation. The variation of Δ? with coverage is stronger than linear. The isosteric heats of adsorption as derived from adsorption isotherms recorded via Δ? compared well with the results of the analysis of the thermal desorption spectra.     

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.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.     

Hydrogen on W(100): temperature dependence of LEED and angle-resolved ESD

For hydrogen adsorption on W(100), the evolution of the c(2 × 2) LEED intensities and of the H⁺ ESD signal with H coverage have been investigated for various adsorption and annealing temperatures. Striking changes have been found for the half-order LEED intensities in the temperature range 140–360 K, in agreement with other workers, where the H⁺ signal showed only minor differences. The maxima of the LEED and the ESD intensities, however, occurred at the same exposure throughout this range (≈25% of saturation coverage). A temperature dependent variation of the height of the H⁺ maximum was observed which was reversible up to the desorption temperature of the β₂ hydrogen phase. The H⁺ ESDIAD lobe was found to have a polar FWHM of about 21°, independent of temperature between 140 and 450 K, and without any azimuthal dependence. These results provide evidence for the assumption that the observable H⁺ ions desorb from reconstructed sites. The number of these sites depends on temperature and hydrogen coverage, as shown by the change of the H⁺ current with these parameters. The transition from H on reconstructed to H on unreconstructed sites is of the order-order type; the energy difference between the two different adsorbate situations is about 135 meV/site at the quarter coverage. The consistency of the results and conclusions with a bridge-site model for H adsorption is shown. Elastic interactions lead to agglomeration of adsorbed H. The azimuthal isotropy of the ESDIAD lobes is interpreted by a superposition of emission from various types of bridge-sites which smear out the anisotropy expected for individual bridge-sites.     

The role of adsorbed sulfur in the H2D2 equilibration reaction on Pt single crystals

The H₂D₂ equilibration on Pt single crystals was investigated under intermediate pressure (100–400 Torr) and temperature (50–250°C), as a function of sulfur coverage. On Pt(110) and Pt(111), adsorbed sulfur modifies the kinetic parameters, activation energy and pre-exponential factor; the latter depends on the temperature on Pt(110) only. The clean Pt(110) face was found to be 5 times more active than the clean Pt(111). On both faces, adsorption of sulfur induces electronic effects on the neighbouring reactional sites. The difference in the behaviour of the two faces and a clear influence of the arrangement of the adsorbed sulfur atoms, deduced from LEED diagrams, tend to prove the structure dependency of the H₂D₂ reaction. A consistent reaction mechanism could be proposed, involving the dissociative adsorption and surface recombination of hydrogen and deuterium, and the reaction between adsorbed molecules for high sulfur coverages. The value of the sulfur coverage which makes the platinum inactive towards H₂D₂ is lower for the (111) than for the (110) orientation; this is in correlation with the roughness of the surface; the denser at atomic scale a surface is, the further is the extent of the lateral interactions due to adsorbed sulfur.     

Flash desorption and equilibration of H2 and D2 on single crystal surfaces of platinum

The adsorption and flash desorption of hydrogen and the equilibration of H₂ and D₂ has been studied on the (110), (211), (111) and (100) planes of platinum. Desorption from Pt (211), a stepped surface composed of (111) and (100) ledges, yields a desorption spectrum which apparently is a composite of desorption from the individual ledges. Pt (110) is quite similar to the tungsten structural analog, W (211), in that both yield two-peak desorption spectra, and on both planes adsorption kinetics are dramatically different for filling of the two states. On all four planes adsorption kinetics are apparently proportional to (1 ? θ)², and estimates of the initial sticking probabilities show them to decrease in the order: (110) > (211) > (100) > (111). Equilibration activity follows approximately the same order [(110) > (211) > (111) > (100)] with a factor of ~ 5 difference between the most and least active planes; no extraordinary activity is observed for the stepped surface, Pt(211). Below ~ 570 K equilibration of H₂ and D₂ is activated by less than 2 kcal/mole with the magnitude dependent on the specific face, and above this temperature the reaction is nonactivated. The non-activated case apparently results from absorption followed by statistical mixing on the surface. Calculated rates for HD production per cm² based on this model are in excellent agreement with the experimental values for Pt(110) and Pt(211), and in somewhat poorer agreement in the case of Pt (111) and Pt (100). This latter is probably due to the greater inaccuracy in the values of the sticking coefficients on these planes.     

The adsorption of hydrogen on iron; A surface orbital modified occupancy — bond energy bond order calculation

A Surface Orbital Modified Occupancy — Bond Energy Bond Order (SOMO-BEBO) model calculation of hydrogen adsorption on iron is presented. This calculation represents a novel approach to the CFSO-BEBO method in that the calculation is correlated in a consistent way with the thermal desorption spectra of the hydrogen-iron system. Heats of molecular adsorption calculated are ?32.88, ?35.68 and ?49.57 kJ/mol for the iron (110), (100), and (111) surfaces, respectively. Heats of dissociative adsorption calculated are ?54.40, ?75.30 and ?87.90 kJ/mol for the three states on the iron (111) surface; ?51.21 and ? 73.62 kJ/mol for the two states on the iron (100) surface; and ?63.78 kJ/mol for the one state on the iron (110) surface. Activation energies for dissociative adsorption were found to be small or zero for the iron (111) surface while non-zero activation energies of 49.27 and 45.05 kJ/mol were calculated for the iron (100) and (110) surfaces, respectively. The FeH single-order bond energy has been calculated to be 298.2 kJ/mol. The radius of the hydrogen surface atom has been estimated to be 1.52 × 10^?10 m consistent with the expected size of an H^? ion. The elimination of certain surface sites for molecular adsorption as a result of the ferromagnetism of iron is suggested by the calculation. The reason for the absence of well defined LEED patterns for hydrogen adsorption on the iron (111) and (100) surfaces [Bozso et al., Appl. Surface Sci. 1 (1977) 103] is explained on the basis of the size of the H^? surface ion. The adsorption of hydrogen on the iron (110) surface is consistent with a relatively stable, small-sized H⁺₂ surface ion giving, therefore, a regular LEED pattern and a positive surface potential upon adsorption of hydrogen on this surface.     

The CO coadsorption and reactions of sulfur,hydrogen and oxygen on clean and sulfided Mo(100) and on MoS2(0001) crystal faces

The chemisorption and reactivity of O₂ and H₂ with the sulfided Mo(100) surface and the basal (0001) plane of MoS₂ have been studied by means of Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). These studies have been carried out at both low (10^?8–10^?5Torr) and high (1 atm) pressures of O₂ and H₂. Sulfur desorbs from Mo(100) both as an atom and as a diatomic molecule. Sulfur adsorbed on Mo(100) blocks sites of hydrogen adsorption without noticeably changing the hydrogen desorption energies. TDS of ¹⁸O coadsorbed with sulfur on the Mo(100) surface produced the desorption of SO at 1150 K, and of S, S₂ and O, but not SO₂. A pressure of 1 × 10^?7 Torr of O₂ was sufficient to remove sulfur from Mo(100) at temperatures over 1100 K. The basal plane of MoS₂ was unreactive in the presence of 1 atm of O₂ at temperatures of 520 K. Sputtering of the MoS₂ produced a marked uptake of oxygen and the removal of sulfur under the same conditions.     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.     

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.     

The adsorption and reaction of H2O on clean and oxygen covered Ag(110)

The adsorption and reaction of water on clean and oxygen covered Ag(110) surfaces has been studied with high resolution electron energy loss (EELS), temperature programmed desorption (TPD), and X-ray photoelectron (XPS) spectroscopy. Non-dissociative adsorption of water was observed on both surfaces at 100 K. The vibrational spectra of these adsorbates at 100 K compared favorably to infrared absorption spectra of ice Ih. Both surfaces exhibited a desorption state at 170 K representative of multilayer H₂O desorption. Desorption states due to hydrogen-bonded and non-hydrogen-bonded water molecules at 200 and 240 K, respectively, were observed from the surface predosed with oxygen. EEL spectra of the 240 K state showed features at 550 and 840 cm^?1 which were assigned to restricted rotations of the adsorbed molecule. The reaction of adsorbed H₂O with pre-adsorbed oxygen to produce adsorbed hydroxyl groups was observed by EELS in the temperature range 205 to 255 K. The adsorbed hydroxyl groups recombined at 320 K to yield both a TPD water peak at 320 K and adsorbed atomic oxygen. XPS results indicated that water reacted completely with adsorbed oxygen to form OH with no residual atomic oxygen. Solvation between hydrogen-bonded H₂O molecules and hydroxyl groups is proposed to account for the results of this work and earlier work showing complete isotopic exchange between H₂¹⁶O_(a) and ¹⁸O_(a).     

The low temperature water formation reaction on Pt(111): A static SIMS and TDS study

The formation of water by the reaction of preadsorbed oxygen with hydrogen on a Pt(111) surface has been characterized, using secondary ion mass spectroscopy, below the desorption temperature of H₂O (180 K). The concentration of chemisorbed water was monitored during the reaction by following the SIMS H₃O⁺ signal. Reaction profiles were measured over a temperature range of 120 to 153 K, and an H₂ pressure range of 10^-9 to 10^-6 Torr. Under all conditions the reaction profiles were characterized by an induction time, a region of rapid reaction, and finally a steady decline in the rate. In the rapid region, an overall activation energy of 2.9 ± 0.3 kcalmol^-1 and a half-order H₂ pressure dependence were observed. At low initial oxygen concentrations the induction time increased and the maximum rate decreased. The reaction was slow in the absence of gas phase hydrogen, even when the surface coverage of hydrogen was relatively high. Water and hydrogen thermal desorption spectra, measured after stopping the reaction by removal of gas phase hydrogen, were complex functions of the H₂ exposure, exhibiting several peaks between 170 and 400 K. However, after an exposure large enough to drive the reaction to completion, only one H₂O peak at 173 K and one H₂ peak at 350 K were observed. The results indicate that only a fraction of the total H(a) on the surface was readily available for reaction during H₂ exposure at T ? 153 K. the remainder either recombined to form H₂ or reacted with O(a) during the thermal desorption ramp. There is good evidence for a surface rearrangement during the induction period. A model is proposed which involves the formation of water clusters that accelerate the rate.     

The NO + CO reaction on Pt(100)

The interaction of NO with CO and with H₂ on Pt(100) was studied by temperature programmed desorption (TPD), isothermal desorption mass spectrometry, and low energy electron diffraction (LEED), TPD of NO and CO coadsorbed at 120 K yields almost complete reaction with both N₂ and CO₂ products desorbing as sharp, simultaneous peaks at ≈ 410 K. with full widths at half maximum as narrow as 3 K. Isothermal desorption mass spectrometry yields N₂ and CO₂ rates that exhibit a maximum with time. Both experiments indicate that the reaction mechanism is autocatalytic. Annealing NO-CO adlayers formed at 120 K to temperatures above 300 K causes the subsequent N₂ and CO₂ TPD peaks to broaden.'TPD of NO coadsorbed with H₂ yields sharp N₂ and H₂O product peaks that closely resemble the N₂ and CO₂ peaks observed in the NO + CO reaction. LEED experiments during TPD and isothermal desorption showed that the (1 × 1) → hex substrate phase transformation sometimes accompanies desorption of N₂ and CO₂. The TPD and isothermal desorption results can be fit by two simple models: chemical autocatalysis, in which an intermediate chemical species participates in a “chain propagation” reaction, and structural autocatalysis, which involves the formation of a reactive intermediate structure involving Pt atom displacements.     

Adsorption studies on a stepped Pt(111) surface: O2, CO,C2H4, C2N2

A comparative study of the adsorption of several gases on a Pt(S)-[9(111) × (111)] surface was performed using LEED, Auger spectroscopy, flash desorption mass spectrometry and work function changes as surface sensitive techniques. Adsorption was found to be generally less ordered on the stepped surface than on the corresponding flat surface with the exception of the oxygen, where r well ordered overlayer in registry over many terraces was found. Absolute coverages were determined from flash desorption experiments for O₂, CO and C₂N₂. Similar values were obtained as on flat Pt surfaces. Two different surface species seem to be formed upon adsorption of C₂H₄ depending on the adsorption temperature. Contrary to reports from Pt(111) surfaces conversion between the two surface species is heavily restricted on the stepped surface. Work function changes revealed nonlinear adsorbate effects where the adsorbate is electronegative with respect to the substrate. Various adsorption models are discussed in the light of complementary experimental evidence. The results of this study are compared with data available from flat Pt surfaces and possible influences of steps are discussed. No general trends, however, emerge from this comparison and it seems that eventual influences of steps have to be considered individually for every adsorbate.     

Electrocatalytic activity of a Gd2Ti0.6Mo1.2Sc0.2O7-δ anode towards hydrogen and methane electro-oxidation in a solid oxide fuel cell

Mixed conducting oxide anodes are being considered for the direct utilisation of natural gas in high temperature fuel cells. This work refers to the electrochemical characterization of the pyrochlore Gd₂Ti_0.6Mo_1.2Sc_0.2O_7-δ (GTMS) as anode in a solid oxide fuel cell running in low humidity hydrogen or methane. The electro-oxidation reaction was investigated using impedance spectroscopy, potentiostatic measurements and cyclic voltammetry. Kinetic data were obtained for different fuels in the temperature range 845–932 °C. In a methane-fuelled cell, steam reforming appears to be the rate-limiting step. The overall polarisation resistance of the anode under open circuit conditions at 932 °C was 6.86 Ω·cm² in 97% H₂/3% H₂O, and 43 Ω·cm² in 97% CH₄/3% H₂O. For a 97% fuel-3% H₂O/GTMS//YSZ-Al₂O₃//Pt/air cell, the maximum power output at 932 °C was 9.5 mW/cm² and 1.8 mW/cm² in hydrogen and methane, respectively. First investigations on this type of electrode material show unidentified peaks on XRD spectra after electrochemical test, which indicate GTMS instability under experimental conditions. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Low-energy 3He+ ion scattering spectroscopy studies of D2 adsorption on W(211)

Direct physical evidence for occupation of a trough site by the β₂ state of deuterium adsorbed on W(211) has been obtained by angle-resolved ³He⁺/D(ads) ion-scattering spectroscopy (ISS) in combination with LEED/Auger. The W(211) surface is composed of close-packed 〈111〉 rows of W atoms separated by a wide channel. Previous thermal desorption studies have shown two clearly resolved hydrogen states: β₁ desorbing with a temperature maximum of ca. 60°C, and β₂ at ca. 400°C. Analyses of flash desorption, work-function, adsorption kinetics, stoichiometry and mixed adsorption further indicated that the more tightly bound β₂ form occupies a deep-trough position. In the present study, ISS polar-angle profiles were taken at an incident energy of 306 eV. With only the β₂ state populated, a ³He⁺ beam parallel to the close-packed 〈111〉 rows was found to scatter from D(ads) with a cutoff angle close to grazing incidence while for the perpendicular direction D(ads) scattering is observed only for angles greater than 18° away from grazing incidence. These measurements are consistent with the corrugated W(211) geometry and with the proposed β₂-D trough-site model.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.