Thermal decomposition of CO on a stepped Ni surface

The adsorption-desorption behaviour of CO on the stepped Ni(S) [5(111) × (11̄0)] and the smooth Ni(111) plane are compared by using LEED, thermal flash desorption and AES. Above room temperature flash desorption from the Ni(111) face yields a single α peak characteristic of molecularly adsorbed CO whereas from the stepped surface in addition to the a peak α second desorption peak (β2) appears around 550°C which is assigned to associative CO desorption. If carbon and oxygen are separately chemisorbed on Ni(111) associative desorption of CO leads to a desorption peak around 350° C. It is concluded that steps lower the activation energy for CO decomposition but increase the activation energy for associative desorption.     

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)] face

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)) face has been studied by flash desorption, LEED and AES. On adsorbing oxygen the (1 × 1) LEED pattern of the clean face was transformed into a (2 × 2) pattern. A lower limit of the initial sticking coefficient of 0.06 and a saturation coverage of approximately 0.5 monolayer were determined. The flash desorption spectra exhibited two not completely resolved desorption maxima. From the peak temperatures the activation energies of desorption were estimated to be 41 and 49 kcal/mole. Under the same experimental conditions some experiments were done on a smooth (111) Pt face. However, the results did not differ significantly from those obtained on the stepped surface. In addition on the smooth (111) face the adsorption of oxygen activated in a high frequency discharge was studied. Oxidation was not observed beyond the chemisorption layer which is formed from molecular oxygen.     

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 NO with a Ni (111) surface

The interaction of NO with a Ni (111) surface was studied by means of LEED, AES, UPS and flash desorption spectroscopy. NO adsorbs with a high sticking probability and may form two ordered structures (c4 × 2 and hexagonal) from (undissociated) NO_ad. The mean adsorption energy is about 25 $\text{kcal}\text{mole}$. Dissociation of adsorbed NO starts already at ?120°C, but the activation energy for this process increases with increasing coverage (and even by the presence of preadsorbed oxygen) up to the value for the activation energy of NO desorption. The recombination of adsorbed nitrogen atoms and desorption of N₂ occurs around 600 °C with an activation energy of about 52 $\text{kcal}\text{mole}$. A chemisorbed oxygen layer converts upon further increase of the oxygen concentration into epitaxial NiO. A mixed layer consisting of N_ad + O_ad (after thermal decomposition of NO) exhibits a complex LEED pattern and can be stripped of adsorbed oxygen by reduction with H₂. This yields an N_ad overlayer exhibiting a 6 × 2 LEED pattern. A series of new maxima at ≈ ?2, ?8.8 and ?14.6 eV is observed in the UV photoelectron spectra from adsorbed NO which are identified with surface states derived from molecular orbitals of free NO. N_ad as well as O_ad causes a peak at ?5.6 eV which is derived from the 2p electrons of the adsorbate. The photoelectron spectrum from NiO agrees closely with a recent theoretical evaluation.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Absolute coverage of C2H2 and C2H4 on Pt(111)

Quantitative XPS measurements have been performed in order to determine the absolute coverage of acetylene and ethylene adsorbed on Pt(111) showing a 2 × 2 LEED pattern. This LEED pattern has so far been attributed to a 2 × 2 superstructure with a coverage of 0.25. A quantitative evaluation of the C(1s) peak intensities for these adsorbed layers in comparison with adsorbed CO shows that the coverage is 0.5 instead of 0.25. Therefore the 2 × 2 LEED pattern should be assigned to a 2 × 1 superstructure in three domains rather than a 2 × 2 superstructure.     

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.     

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.     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.     

Chlorine monolayers on the low-index faces of silver

Chlorine chemisorption layers were obtained on the (100), (110) and (111) faces of silver single crystals by means of the reaction with dichloroethane. The structure and stability of the surface phases was studied mainly by LEED and Auger spectroscopy. On the (100) face, a c(2 × 2) superstructure was found at all coverages, which was interpreted as a reconstructed layer with a structure similar to that of the AgCl (100) planes. On the other two faces, different superstructures were observed, depending on the coverage. At low coverages, (2 × 1) and (√3 × √3)-R 30° superstructures were found on the (110) and (111) faces, respectively, which seem to be better interprétable as reconstructed layers. At maximum coverages, c(4 × 2) and (3 × 3) superstructures were observed respectively on the two faces. These phases were interpreted as mixed layers with a packing of the silver and chlorine atoms similar to that of the AgCl (111) planes. The proposed models are in agreement with the different thermal stabilities of the layers. The models of the maximum-coverage structures correspond to about the same chlorine amount on the three faces, in agreement with the Auger results. The structures are also discussed in relation to the known epitactic relations for the growth of AgCl on silver.     

Equilibrium surface segregation of dissolved nonmetal atoms on iron(100) faces

At elevated temperatures equilibria of surface segregation X (dissolved) = X (adsorbed) have been studied for the nonmetal atoms X = C, N and S. Iron single crystals with (100)orientation have been doped with different concentrations of solute atoms (in the range about 10–100 wt ppm). The samples were introduced into the UHV chamber, cleaned and then heated to temperatures in the α-solid solution range. The surface concentration of the segregated nonmetal atoms was observed by AES for different bulk concentrations in dependence of the temperature. The LEED pattern was also observed during segregation equilibrium at temperatures up to about 750° C. The LEED patterns indicate a c(2 × 2) structure for carbon and nitrogen as well as for sulfur. The temperature dependence of the surface concentration for carbon on Fe(100) can be described by a Langmuir-McLean equation, an average segregation enthalpy of ?85 kJ/mol°C is obtained. Since N₂ desorption occurs the nitrogen segregation is in virtual equilibrium only at temperatures <500°C. The equilibrium surface concentration of sulfur on α-iron is virtually independent of the solute concentration and the temperature: there is always a saturated layer of sulfur on the (100) faces, even at small bulk concentrations. Since the thermodynamic activity of the nonmetal atoms is well defined in the segregation studies (except nitrogen at higher temperatures) , the results can be correlated with studies in gas atmospheres at atmospheric pressure. The relations to the kinetics of the carburization and the nitrogenation of iron are discussed and the influence of sulfur on these reactions.     

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.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

Benzene adsorption on nickel (100) and (111) faces studied by leed and high resolution electron energy loss spectroscopy

Studies of benzene (C₆H₆ and C₆D₆) adsorption have been performed by high resolution electron energy loss spectroscopy (HRELS) and LEED experiments on nickel (100) and (111) single crystal faces at room temperature. Chemisorption induces ordered structures, c(4 × 4) on Ni(100) and (2√3 × 2√3)R30° on Ni(111), and typical energy loss spectra with 4 loss peaks accurately identified with the strongest infrared vibration bands of the gazeous molecules. Benzene chemisorption preserves the aromatic character of the molecule and involves respectively 8 nickel surface atoms on the (100) face and 12 on the (111) face by adsorbed molecule. The interaction takes place via the π electrons of the ring. Significant shifts of the CHτ bending and CH stretching vibrations show a weakening of the CH bonds due to the formation of the chemisorption bond and a coupling of H atoms with the nickel substrate.     

Adsorption of CO on Pd single crystal surfaces

Studies of CO adsorption on Pd(110), (210) and (311) surfaces as well as with a (111) plane with periodic step arrays were performed by means of LEED, contact potential and flash desorption measurements. Isosteric heats of adsorption were evaluated from adsorption isotherms. Earlier work with Pd(111) and Pd (100) surfaces is briefly reviewed, yielding the following general picture: The initial adsorption energies vary between 34 and $\text{40}\text{kcal}\text{mole}$ and close similarities exist for the dipole moments, the maximum densities of adsorbed particles and for the adsorption kinetics. At low and medium coverage the adsorbed particles are located at highly symmetrical adsorption sites, whereas saturation is characterized by the tendency for formation of close-packed layers.     

The sorption of CO and O on Ni (111) studied by leed and iss

The adsorption of CO and O on Ni (111) was studied by low-energy ion scattering (ISS) and low-energy electron diffraction (LEED). For the ordered (√7/2) × (√7/2) R19.1° CO layer ion scattering gives a coverage greater than $\text{1}\text{2}$ monolayer, and for the (2 × 2) O layer a coverage of $\text{1}\text{4}$ monolayer. The CO is non-dissociatively adsorbed, with the C bound to the Ni. The molecules are oriented parallel to the surface normal. Island formation at lower CO coverages is possible.     

Adsorption of glycine on a NiAl(1 1 0) alloy surface

The adsorption and desorption of glycine (NH₂CH₂COOH), vacuum deposited on a NiAl(1 1 0) surface, were investigated by means of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), temperature-programmed desorption, work function (Δφ) measurements, and ultraviolet photoelectron spectroscopy (UPS). At 120 K, glycine adsorbs molecularly forming mono- and multilayers predominantly in the zwitterionic state, as evidenced by the UPS results. In contrast, the adsorption at room temperature (310 K) is mainly dissociative in the early stages of exposure, while molecular adsorption occurs only near saturation coverage. There is evidence that this molecularly adsorbed species is in the anionic form (NH₂CH₂COO⁻). Analysis of AES data reveals that upon adsorption glycine attacks the aluminium sites on the surface. On heating part of the monolayer adsorbed at 120 K is converted to the anionic form and at higher temperatures dissociates further before desorption. The temperature-induced dissociation of glycine (<400 K) leads to a series of similar reaction products irrespective of the initial adsorption step at 120 K or at 310 K, leaving finally oxygen, carbon and nitrogen at the surface. AES and LEED measurements indicate that oxygen interacts strongly with the Al component of the surface forming an “oxide”-like Al-O layer.     

Electron stimulated oxidation of GaAs,studied by quantitative auger electron spectroscopy

The oxidation properties of the clean polar (111) faces of GaAs, prepared by Ar⁺ bombardment and proper annealing, are investigated. Considering the adsorbed layer as a continuum and using empirical values for the escape depth of the Auger electrons from literature, the coverage of oxygen on these faces is quantitatively determined. For a coverage of up to 10% of a monolayer the sticking coefficients are about 10^?3 for the ($\text{111}$) As face and about 10^?4 for the (111) Ga face, respectively. They decrease rapidly with increasing coverage. The oxidation is strongly stimulated by electron irradiation causing dissociation of the oxygen which is originally adsorbed in molecular form. In this way a compact oxide layer is formed which shows As depletion as a result of sublimation of As₄O₆ and a chemical shift of the Ga Auger peaks is observed. The cross section for the O₂ dissociation is calculated to be 1.8–2.5 Ų depending on electron energy.     

Adsorption of NO and CO on a Ru(1010) surface

A combination of modern surface measurement techniques such as LEED, AES and Thermal Desorption Spectroscopy were used to study the chemisorptive behavior of NO and CO on a $\text{(10}\text{1}\text{0)Ru}$ surface. The experimental evidence strongly favors a model in which NO adsorbs and rapidly dissociates into separate nitrogen and oxygen adsorbed phases, each exhibiting ordered structures: the C(2 × 4) and (2 × 1) structures at one-half and full saturation coveilage, respectively. At temperatures as low as 200°C, the nitrogen phase begins to desorb, and continuous exposure to NO in this temperature range results in an increasing oxygen coverage until the surface is saturated with oxygen and no further NO dissociation can take place. The nitrogen desorption spectrum depends strongly on coverage and exhibits several peaks which are related to structure of the adsorbed phase. There is evidence that once the surface is saturated with the dissociated NO phase further NO adsorption occurs in a molecular state. Carbon monoxide adsorbs in a molecular state and does not exhibit an ordered structure. The implications of the results with respect to the catalytic reduction of NO by H₂ and CO and the N₂ selectivity of Ru catalysts are discussed.