ESDIAD and LEED studies of the clean TiO2(100) surface

Electron-stimulated desorption ion angular distribution (ESDIAD) and LEED were used to investigate the structure changes at the TiO₂(100) surface. The angular distribution of O⁺ ions from the (1 × 3) reconstructed surface is consistent with the microfacet model proposed from X-ray diffraction and STM studies. The (1 × 3) reconstructed surface can be transferred back to the (1 × 1) surface after annealing at 950 K in oxygen, through a stage where the surface consists of (1 × 1) and (1 × 3) domains which are smaller than the coherent width of the LEED electron beam. Evidence for surface reconstruction on the (1 × 1) surface is also found.     

Decomposition of carbon monoxide on a (110) nickel surface

New investigations of the (110) nickel/carbon monoxide system have been made using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), mass spectroscopy and work function measurements. Room temperature adsorption of CO on the surface was reversible with the CO easily removable by heating in vacuum to 450°K. The CO formed a double-spaced structure on the surface which, however, was unstable at room temperature for CO pressures less than 1×10^?7 torr. Work function changes greater than + 1.3 eV accompany this reversible CO adsorption. Irreversible processes leading to the build-up of carbon, and under certain circumstances oxygen, on the surface were the primary concern of the measurements reported here. These processes could be stimulated by the electron beams used in LEED and AES, or by heating the clean surface in CO. The results of AES investigations of this carbon (and oxygen) build-up, together with CO desorption results could be explained on the basis of two surface reactions. The primary reaction was the dissociation of chemisorbed CO leaving carbon and oxygen atomically dispersed on the surface. The second reaction was the reduction of the surface oxygen by CO from the gas phase. The significance of the dissociation reaction to COdesorption studies is discussed.     

A UPS and LEED/Auger study of adsorbates on Fe(110)

Ultraviolet photoemission spectroscopy (UPS) and LEED/Auger were used to study adsorbed species of C, N, O, S, CO, NO, and C₂H₂ on Fe(110). The complicated “carbon ring” LEED patterns were shown to be due to atomic carbon and/or nitrogen. Molecular nitrogen does not stick at or above room temperature on Fe(110). The optical excitation probability of the 3p electrons of segregated sulphur is found to have a Cooper minimum aroundhω=40.8 eV. Carbon monoxide chemisorbs molecularly at room temperature and then dissociates slowly. Only dissociative CO adsorption was observed atT=385 K. Acetylene also adsorbs molecularly but does not dissociate at room temperature. By contrast, nitric oxide chemisorption is completely dissociative at room temperature.     

A LEED and AES study of the structure,debye temperature,and oxidation of the (111) crystal face of thorium

The structure, and reactivity towards O₂ and CO, of the (111) crystal face of a single crystal of high purity thorium metal was studied using low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES). After the sample was cleaned in vacuum by a combination of ion bombardment and annealing, a (1 × 1) LEED pattern characteristic of a (111) surface was obtained. Extended annealing of the cleaned sample at 1000 K produced a new LEED pattern characteristic of a (9 × 9) surface structure. A model of a reconstructed thorium surface is presented that generates the observed LEED pattern. When monolayer amounts of either O₂ or CO were adsorbed onto the crystal surface at 300 K, no ordered surface structures formed. Upon heating the sample following these exposures the (111) surface structure was restored accompanied by a reduction in the amount of surface carbon and oxygen. With continued exposure to either O₂ or CO and annealing, a new LEED pattern developed which was interpreted as resulting from the formation of thorium dioxide. Debye-Walter factor measurements were made by monitoring the intensity of a specularly reflected electron beam and indicated that the Debye temperature of the surface region is less than it is in bulk thorium. Consequently, the mean displacement of thorium atoms from their equilibrium positions was found to increase at the surface of the crystal. The presence of chemisorbed oxygen on the crystal surface affected the Debye temperature, raising it significantly.     

Oxygen chemisorption and the carbon monoxide-oxygen interaction on Ru(101)

The adsorption of oxygen and the interaction of carbon monoxide with oxygen on Ru(101) have been studied by LEED, Auger spectroscopy and thermal desorption. Oxygen chemisorbs at 300 K via a precursor state and with an initial sticking probability of ~0.004, the enthalpy of adsorption being ~300 kJ mol^?1. As coverage increases a well ordered ¦11,30¦ phase is formed which at higher coverages undergoes compression along [010] to form a ¦21,50¦ structure, and the surface eventually saturates at 0 ~ $\text{8}\text{9}$. Incorporation of oxygen into the subsurface region of the crystal leads to drastic changes in the surface chemistry of CO. A new high; temperature peak (γ CO, E_d ~ 800 kJ mol^?1) appears in the desorption spectra, in addition to the α and β CO peaks which are characteristic of the clean surface. Coadsorption experiments using ¹⁸O₂ indicate that γ CO is not dissociatively adsorbed, and this species is also shown to be in competition with β CO for a common adsorption site. The unusual temperature dependence of the LEED intensities of the ¦11,30¦-O phase and the nature of α, β, and β CO are discussed. Oxygen does not displace adsorbed CO at 300 K and the converse is also true, neither do any Eley-Rideal or Langmuir-Hinshelwood reactions occur under these conditions. Such processes do occur at higher temperatures, and in particular the reaction CO(g) + O(a) → CO₂(g) appears to occur with much greater collisional efficiency than on Ru(001). The oxidation of CO has been examined under steady state conditions, and the reaction was found to proceed with an apparent activation energy of 39 kJ mol^?. This result rules out the commonly accepted explanation that CO desorption is rate determining, and is compared with the findings of other authors.     

Ion angular distributions in electron stimulated desorption: Oxygen and CO on W(111)

The ion angular distributions resulting from electron stimulated desorption (ESD) of oxygen and carbon monoxide chemisorbed on a tungsten (111) crystal have been determined. The O⁺ ions released during ESD of adsorbed oxygen exhibit three-fold symmetric angular distributions in orientational registry with the W(111) substrate. The CO⁺ and O⁺ ions released during ESD of a monolayer of CO are desorbed normal to the (111) surface. Models for both oxygen and CO adsorption are discussed. The data for CO are consistent with adsorption of CO in “standing up” carbonyl structures in the virgin and α-CO binding states.     

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.     

Ellipsometric study of oxygen adsorption and the carbon monoxide-oxygen interaction on ordered and damaged Ag(111)

The adsorption of oxygen on Ag(111) has been studied by ellipsometry in conjunction with AES and LEED. The oxygen pressure varied between 10^?5 and 10^?3 Torr and the crystal temperature between room temperature and 250° C. Changes in the Auger spectrum and the LEED pattern upon oxygen adsorption are very small. Oxygen coverages were derived from the changes in the ellipsometric parameter Δ. At room temperature a maximum coverage is reached within a few minutes. Its value increases with the damage produced by the preceding argon ion bombardment. The sticking coefficient derived from the initial rate of Δ-change amounts to 3 × 10^?5 for well-annealed surfaces and 2.5 ? 5 × 10^?4 for damaged surfaces. After evacuation no desorption takes place. Other types of adsorption, associated with much larger changes in Δ, were observed upon bombardment with oxygen ions and with oxygen activated by a hot filament. The reaction of CO with adsorbed oxygen was studied ellipsometrically at room temperature in the CO pressure range 10^?7–10^?6 Torr. The initial reaction rate is proportional to the CO pressure. The reaction probability (number of oxygen atoms removed per incident CO molecule) is 0.36.     

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.     

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.     

Effects of adsorbed carbon and oxygen on the chemisorption of H2 and Co on Mo(100)

The deposit of carbon and oxygen adatoms on Mo(100) was characterized by AES and LEED. Carbon was introduced by the thermal cracking of ethylene; several ordered structures were observed as a function of coverage with carbon atoms residing on four-fold sites. The Mo(100)—O system exhibited two different sequences of LEED patterns depending on the adsorption temperature of oxygen. The effects of adsorbed carbon and oxygen on the chemisorption properties of Mo(100) was investigated by FDS. The presence of either carbon or oxygen severely hindered the ability of Mo(100) to dissociatively adsorb hydrogen or carbon monoxide. The amount of CO dissociated was directly related to the available four-fold sites on the carbide surfaces. The molecular adsorption of CO was not significantly affected by the adlayers. It was found that one monolayer of adsorbed oxygen reduced the binding energy of molecular CO considerably more than the same amount of adsorbed carbon. A continuous shift in the binding energy of CO with the C/O ratio on the surface was observed.     

Oxygen chemisorption,surface oxidation,and the oxidation of carbon monoxide on cobalt (0001)

Oxygen chemisorbs on clean Co(0001) at 300 K with an initial sticking probability of ~0.3. The chemisorbed overlayer (which is very reactive towards CO) readily undergoes conversion to cobalt oxide, even at room temperature. This transformation is accelerated at higher temperatures, and the oxygen uptake rate falls as CoO growth proceeds. At a certain point, however, the uptake rate rises sharply, and this behaviour is ascribed to nucleation and growth ofCo₃O₄. This interpretation is consistent with the available Δφ, Auger, LEED, and reactivity data. Thus Δφ changes sign as lattice penetration by the ad sorbed oxygen takes place, and this is accompanied by a shift and broadening of the O(KLL) Auger signal. LEED indicates the epitaxial growth firstly of CoO(111) and then, at higher oxygen exposures, of Co₃O₄(111). At 300 K CO rapidly reduces the Co₃O₄ surface back to CoO, and the oxidation/reduction behaviour by O₂/CO appears to be completely reversible. Steady-state measurements yield a value of 19 ± 7 kJ mol^?1 for the activation energy to CO₂ production from CO + O₂. Earlier photoelectron spectroscopic studies by other authors are considered in the light of these results.     

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.     

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.     

Interaction of CO with surface PdZn alloys

The adsorption and bonding configuration of CO on clean and Zn-covered Pd(1 1 1) surfaces was studied using low energy electron diffraction (LEED), temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). LEED and TPD results indicate that annealing at 550 K is sufficient to induce reaction between adsorbed Zn atoms and the Pd(1 1 1) surface resulting in the formation of an ordered surface PdZn alloy. Carbon monoxide was found to bond more weakly to the Zn/Pd(1 1 1) alloy surfaces compared to clean Pd(1 1 1). Zn addition was also found to alter the preferred adsorption sites for CO from threefold hollow to atop sites. Similar behavior was observed for supported Pd-Zn/Al₂O₃ catalysts. The results of this study show that both ensemble and electronic effects play a role in how Zn alters the interactions of CO with the surface.     

Surface reconstruction of Cu (111) upon oxygen adsorption

Low-energy He⁺ ion scattering (IS) in combination with AES, LEED and work function measurements has been applied for the determination of surface reconstruction of Cu(111) upon oxygen adsorption. IS data clearly indicate that oxygen is not significant incorporated into the bulk at room temperature adsorption, however the surface shows reconstruction by displacement of Cu atoms by 0.3 Å. The disappearance of structure of both Cu_IS and O_IS in the “?_in pattern” demonstrate the development of a disordered layer of reconstruction centres. At saturation coverage, a rough and dis-ordered oxygen-copper surface layer is present.     

Reduction of nitric oxide on the carbon pretreated Rh{331} single crystal surface; evidence for molecular CN− formation

The chemisorption of NO on the carbon pretreated Rh{331} single crystal surface has been investigated by XPS, LEED and SIMS. The carbon overlayer was prepared by dehydrogenation of chemisorbed C₂H₄. Results of NO adsorption at room temperature show that surface carbon blocks adsorption sites that normally coordinate molecular NO_ADS and its dissociated products, N_Ads and O_Ads, as determined by comparing to experiments performed on clean Rh{331}. Heating the surface which contains NO_Ads, n_Ads, O_Ads and C_Ads, induces a series of chemical reactions starting with the dissociation of molecular NO_Ads. Above 400 K, the C_Ads and N_Ads atoms combine to form CN^?. The formation of the latter species is confirmed by the temperature evolution of the Rh₂CN⁺ and CN^? SIMS ion yields. The C_Ads species also reacts with O_Ads to produce CO and/or CO₂. These processes occur preferentially over the desorption of N₂ and O₂. In general, it is demonstrated that by using the XPS and SIMS methods, it is possible to identify the reaction species present on the surface at any given temperature and to unravel rather complex reaction pathways.     

Interaction of O2 with low index faces of α-CuZn

The adsorption of O₂ and initial step of oxidation have been investigated, mainly at room temperature, for three different α-CuZn (75%Cu/25%Zn) surfaces ((110), (100) and (111)) by XPS. XAES, LEED, CPD and HREELS. No superstructures were detected on the LEED patterns during O₂ admission for the three faces, and from the beginning of adsorption Zn segregated to the surface. For (110), the interaction of oxygen follows the sequence: (1) dissociative chemisorption (up to ~ 20 L), accompanied by an increase of the work function and a single site occupancy as revealed by HREELS; (2) nucleation of ZnO only, indicated by a decrease of the work function, a shift of the Zn L₃M₄₅M₄₅ Auger transition and an emergence of a vibration at 550 cm^?1. corresponding to the surface phonon of ZnO. The (111) face follows the same scheme, except that the sticking coefficient for oxygen is very low. For (100), it is clear that two states of oxygen exist simultaneously, even at the beginning, as revealed by HREELS and CPD measurements. No copper oxides are ever detected, even after heat treatment. In addition, different bonding properties of OH groups on the three surfaces are reported.     

The geometry of CO on Ru(001): Evidence for bending vibrations in adsorbed molecules

As a test of the utility of the ESDIAD method (Electron Stimulated Desorption Ion Angular Distributions) in studies of the geometry of adsorbed molecules, the chemisorption of CO on Ru(001) has been examined. Data previously reported using UPS (ultraviolet photoemission spectroscopy) and EELS (electron energy loss spectroscopy) have indicated that CO is terminally bonded to the Ru surface through the C atom, with the CO axis perpendicular to the surface. The ESDIAD results for CO confirm this orientation; for all CO coverages in the temperature range 90 K to ~ 350 K, the angular distributions of O⁺ and CO⁺ ESD ions are centered about the surface normal. The widths of the ion beams are temperature dependent; for both O⁺ and CO⁺, the half widths at half maximum, α, of the ion cones are ~16° at 300 K, and ~12° at 90 K. This temperature dependence, coupled with a simple model calculation, indicates that the dominant factors contributing to the width of the ESD ion beams are the CO surface bending vibrations, i.e., initial state effects. Thus, the data suggest that both the directions and widths of ESDIAD beams are determined largely by the structure and dynamics of the initial adsorbed state.     

Real-time observation of coadsorption layers on Ru(001) using a temperature-programmed ESDIAD/TOF system

For the purpose of utilizing ESDIAD as a real-time probe for surface processes, we have developed an instrument which can measure ESDIAD images and time of flight (TOF) spectra of desorbing ions in temperature-programmed surface processes. TOF measurements are carried out to identify the mass and to determine the kinetic energy distribution of the desorbed ions. This temperature-programmed (TP-) ESDIAD/TOF system was used to observe coadsorption layers of methylamine and CO on Ru(001) which have been previously studied by our group using LEED, TPD and HREELS, also drawing upon a comparison of findings with the coadsorption system of CO and ammonia. ESDIAD images acquired for temperature-programmed surface processes in real time were found to provide new insight into the dynamic behaviour of the coadsorption layers. As to the pure adsorption of ammonia and methylamine, the second and the first (chemisorbed) layers can be easily discriminated in their different ESD detection efficiency due to the difference in neutralization rate. The intensity change of H⁺ ions with temperature shows the process of the decomposition of methylamine to be dependent on CO coverage. The intensity of O⁺ originating from CO changes due to the change of CO adsorption site in the reaction process. The angular distribution of H⁺ ions which correspond to CH2=NH…Ru species appears at 250–300 K in the presence of high CO pre-coverage.