Effect of CO on hydrogen adsorption on palladium

Coadsorption of H₂ and CO on Pd has been studied using TDS and ESD techniques. It has been observed that the presence of 10% CO in the H₂ dosing gas during exposure gives rise to a drastic change in the TDS spectra of H₂ compared to the case when only H₂ is separately adsorbed. Furthermore, significant modifications occur in the ESD energy distribution of CO⁺ and H⁺ as a result of coadsorption of H₂ and CO. These observations are taken as evidence of adsorbate interaction possibly resulting in formation of an HCO surface complex.     

Chemisorption of CO on tungsten (100): Combined flash desorption and electron stimulated desorption study. II

The chemisorption of CO on W(100) at ~ 100K has been studied using a combination of flash desorption and electron stimulated desorption (ESD) techniques. This is an extension of a similar study made for CO adsorption on W(100) at temperatures in the range 200–300K. As in the 200–300 K CO layer, both α₁-CO and α₂-CO are formed in addition to more strongly bound CO species upon adsorption at ~ 100K; the α-CO states yield CO⁺ and O⁺ respectively upon ESD. At low CO coverages, the α₁ and α₂-CO states are postulated to convert to β-CO or other strongly bound CO species upon heating. At higher CO coverages, α₁-CO converts to α₂-CO upon thermal desorption or electron stimulated desorption. There is evidence for the presence of other weakly-bound states in the low temperature CO layer having low surface concentration at saturation. The ESD behavior of the CO layer coadsorbed with hydrogen on W(100) is reported, and it is found that H(ads) suppresses either the concentration or the ionic cross section for α₁ and α₂-CO states.     

Adsorption of hydrogen and carbon monoxide on platinum

TDS spectra and ESD ion energy distributions have been measured for coadsorption of H₂ and CO on recrystallized platinum. Sample exposure to a 90% H₂?10% CO gas mixture results in appearance of structurein both TDS spectra of H₂ and CO. Coadsorption also results in an O⁺ ion energy distribution which is much narrower compared to the distribution resulting from pure CO adsorption. These results are interpreted as evidence for the formation of an HCO surface complex.     

Sum frequency generation and density functional studies of CO-H interaction and hydrogen bulk dissolution on Pd(1 1 1)

CO-H interaction and H bulk dissolution on Pd(1 1 1) were studied by sum frequency generation (SFG) vibrational spectroscopy and density functional theory (DFT). The theoretical findings are particularly important to rationalize the experimentally observed mutual site blocking of CO and H and the effect of H dissolution on coadsorbate structures. Dissociative hydrogen adsorption on CO-precovered Pd(1 1 1) is impeded due to an activation barrier of ∼2.5 eV for a CO coverage of 0.75 ML, an effect which is maintained down to 0.33 ML CO. Preadsorbed hydrogen prevented CO adsorption at 100 K, while hydrogen was replaced from the surface by CO above 125 K. The temperature-dependent site blocking of hydrogen originates from the onset of hydrogen diffusion into the Pd bulk around 125 K, as shown by SFG and theoretical calculations using various approaches. When Pd(1 1 1) was exposed to 1:1 CO/H₂ mixtures at 100 K, on-top CO was absent in the SFG spectra although hydrogen occupies only threefold hollow sites on Pd(1 1 1). DFT attributes the absence of on-top CO to H atoms diffusing between hollow sites via bridge sites, thereby destabilizing neighboring on-top CO molecules. According to the calculations, the stretching frequency of bridge-bonded CO with a neighboring bridge-bonded hydrogen atom is redshifted by 16 cm⁻¹ when compared to bridging CO on the clean surface. Implications of the observed effects on hydrogenation reactions are discussed and compared to the C₂H₄-H coadsorption system.     

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.     

Coadsorption of oxygen and carbon monoxide on tungsten: Desorption spectra,electron stimulated desorption and field emission microscopy

CO/W desorption spectra are characterized by an α state and multiple β states; using electron stimulated desorption (ESD) the α state was shown to comprise two sub-states, α₁ and α₂. In this paper the consecutive interactions of O₂ and CO on W are investigated using ESD, flash desorption and field emission microscopy (FEM).Desorption spectra show that the α-CO state is displaced by O₂, in two stages. The ESD probe provides an identification of the first stage with the removal of the α₁-CO state, and energy analysis of ESD ions reveals a large energy shift (～ ? 1.5 eV) during O₂ coadsorption which can be attributed to an incresae in the α₁-CO WC bond length of ～ 0.15 Å. During this O₂-induced displacement, the two β peaks converge into a single peak at the β₁ position; this is ascribed to adatom interactions in the mixed O and C adlayer. Isotope exchange experiments with ²⁸CO and ³⁶O₂ reveal (i) no exchange in the α-CO states, and (ii) complete exchange in the β-CO states, which is consistent with dissociative adsorption in the latter. The amount of coadsorbed O₂ is estimated from these results, and from FEM data: a full monolayer of O adatoms can be coadsorbed on CO-saturated W, but CO pre-adsorption inhibits the formation of W oxides. The β₁-O₂ (ESD active) state also forms on the CO-covered surface: this state is identical in population, ESD cross section and ion energy distribution to β₁-O₂ on clean W, and retains its identity in the mixed layer (it does not undergo isotopic exchange). CO₂ desorption spectra from the mixed layer were also characterised, complete isotopic scrambling being observed.Pre-exposure of tungsten to O₂ inhibits CO adsorption: a monolayer of O₂ is sufficient to prevent CO adsorption, and at low O₂ coverages, every O₂ molecule preadsorbed prevents one CO molecule from adsorbing. Isotopic exchange is again complete in the β states, and a lateral interaction model for desorption kinetics, based on dissociative adsorption in the β-CO state, quantitatively describes the CO desorption spectra.     

The coadsorption of CO and H2 on Fe(100)

The coadsorption of CO and hydrogen on an Fe(100) surface was studied by temperature programmed desorption and X-ray photoelectron spectroscopy. It was found that CO adsorption blocked the subsequent dissociative adsorption of H₂, although it did not seem to affect the hydrogen binding energy. Preadsorption of hydrogen was observed to reduce the binding energy of CO subsequently adsorbed and to inhibit the dissociation of CO. A new surface species was identified in a coadsorbed layer of CO and hydrogen. This species was evidenced by the formation of a desorption peak for H₂ at 475 K when CO was adsorbed subsequent to H₂ adsorption.     

Evidence for multiple states of hydrogen on palladium

Adsorption of hydrogen on polycrystalline palladium has been investigated using ESD techniques. Although a single thermal desorption peak is observed for H₂ and Pd, total ESD cross section measurements suggest the existence of four distinct sources for desorbing H⁺ and H^? species. The very large cross section associated with the H^? signal along with its behavior during sample heating suggests the possible existence of a molecular precursor state.     

Reactions of small gold cluster cations with propylene, methane, and hydrogen: permissive and competitive coadsorption effects

Coadsorption effects of molecular hydrogen and small hydrocarbons, CH₄ and C₃H₆, on free Au₃ ⁺ and Au₅ ⁺ were investigated in an octopole ion trap under multi-collision conditions. For hydrogen and methane the observations indicate that both molecules coadsorb on the same adsorption site, i.e., the same atom of the cluster. This type of molecular adsorption on free clusters is termed permissive coadsorption, in contrast to competitive coadsorption, in which two molecules compete for the same adsorption site. The latter case was observed for hydrogen and propylene: already trace amounts of propylene were able to completely saturate the clusters preventing the coadsorption of H₂. The size dependent adsorbate coverage is discussed and implications on the cluster structure are deduced from time and temperature dependent reaction measurements.     

On the origin of electron stimulated desorption of H+ from metal surface

The emission of hydrogen ESD ions from polycrystalline Nb is studied experimentally. The results demonstrate clearly that no ESD emission of H⁺ occurs from a pure H adsorbate. However, adsorption of H₂O, present as an impurity in H₂, and H₂ adsorption on Nb preceded by O adsorption, produce strong H⁺ ESD emission. It is shown that Auger ionization of O can account for the increased H⁺ yield and it is postulated that similar effects also occur on other metal surfaces.     

Surface coverage measurements by sims for CO adsorption on a number of metals and for CO and H2S CO-adsorption on Ni(110), (100) and (111)

A detailed study of CO adsorption on Ni(100) utilizing static SIMS and a comparison of the data with surface coverage data from the literature shows that there is a linear relationship between CO coverage and the peak intensity ratios (MCO⁺/M⁺ and M₂CO⁺/M⁺₂) of the CO-containing secondary ions, in the region of coverage below which the adlayer becomes compressed. Adsorption isobares were obtained using the intensity ratios and from these, adsorption isosteres were derjved to give heats of adsorption as a function of coverage. These data are in very close agreement with the literature. Confirmatory data were obtained for this relationship for CO adsorption on polycrystalline Ni, Pd, Pt and Cu and Cu(100). The application of this technique of surface coverage measurements to a study of the extent to which H₂S coadsorption reduces the coverage of adsorbed CO on Ni(110), (100) and (111) shows that these faces are poisoned in the order (100) > (111) > (110). Surface coverage measurements on the non-closepacked (110) face are affected by the apparent insensitivity of SIMS to adsorbates located in the “channels”.     

Adsorption of hydrogen and carbon monoxide on nickel

Ion induced desorption was used to examine the emission of secondary ion clusters during coadsorption of H₂ and CO on nickel. In addition to the expected CO bearing species, a significant NiOH⁺ signal was observed. It is suggested that the source of this cluster ion may be interaction of the parent adsorbed H₂ and CO. Evidence was also found for emission of a negative species of mass 26, presumably C₂H^?₂.     

Carbon monoxide and hydrogen coadsorption on polycrystalline platinum

The coadsorption of carbon monoxide and hydrogen was studied on a polycrystalline platinum foil. In a comparison with single crystal surfaces, the desorption kinetics of the individual species most closely resemble those on Pt(110). In coadsorption there is competition between CO and H₂. Carbon monoxide completely blocks hydrogen adsorption, but on a hydrogen-saturated surface only two-thirds of the carbon nomoxide adsorption is blocked. Shifts in peak temperatures for hydrogen desorption indicate that repulsive interactions between adsorbed CO and H₂ are important, and lead to segregated islands of the two adsorbates. Under some conditions there is also a new low temperature desorption peak for hydrogen which indicates that there are regions on the surface where carbon monoxide and hydrogen are intermixed.     

Adsorption of hydrogen on evaporated cobalt films

Hydrogen adsorption on evaporated Co films has been studied by means of measurements of the surface potential changes that occur during this process, and analysis of the desorption spectrum of hydrogen. It has been observed that hydrogen adsorbed at 78 K on Co films exists in three forms with essentially different electrical properties: atomic, electronegatively polarized β^? form; atomic, electropositively polarized β⁺ form and reversibly adsorbed, molecular, positively polarized α form. The β^? form is not homogeneous from the point of view of the bond energy with the metal surface and consists of the states β_s^? and β^? characterized by activation energy of desorption 10.0 and 18.8 kcal/mol H₂ correspondingly. The Activation energy of desorption of the β⁺ form is low, i.e. 2.1 $\text{kcal}\text{mol}$ H₂.     

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.     

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.     

Surface vibrations of CO on W(100)

High resolution electron-energy-loss spectroscopy has been used to study the surface vibrations of CO on a W(100) surface at 300 K. For small exposures (β-CO) two losses at ～68 meV and ～78 meV are observed. This vibrational spectrum of β-CO is a clear indication of dissociative adsorption with the carbon and oxygen atoms in fourfold coordination sites each. With further exposure to CO two additional losses at 45 meV and 258 meV are observed, which represent the vibration of undissociated α-CO in upright position on top of a W atom. Furtheron results of coadsorption of H₂/CO and O₂/CO on W(100) are reported.     

The use of low energy sims to study the chemisorption of CO on Ni(100) and polycrystalline nickel

Adsorption of CO on Ni(100) has been investigated using secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy at 175 and 295 K. Interaction with polycrystalline nickel was examined at 295, 325 and 365 K. All the secondary ions, Ni⁺, Ni₂⁺, NiCO⁺ and Ni₂CO⁺ show large increases in intensity as CO is adsorbed but there is no simple correlation of the secondary ion species with the sequence of linear and bridge-bonded CO species expected from electron energy loss spectroscopy. Adsorption of CO at 175 K on a hydrogen saturated Ni(100) surface, which is thought to permit only bridge-bonded adsorbed CO, does not result in any enhancement of Ni₂CO⁺. The extent of increases in secondary ion yields after CO adsorption on the nickel surfaces are primarily related to the variations in the heat of adsorption as a function of surface coverage. The presence of more weakly-held species is important in enhancing secondary ion yields.     

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.     

Stability and separation of phases in Pd and Fe exchanged NaX and NaZSM-5 catalysts in Co+H2 reaction

Pd and Fe exchanged NaX and NaZSM-5 catalysts (Pd/Fe=5) were studied. The components formed in the course of hydrogen activation at 720 K and their transformations taking place during treatments in CO+H₂ at 570 and 500 K are described. Pd_xFe, Fe²⁺ ions in octahedral and tetrahedral environments and x-iron carbide components are identified. The bimetallic component is not affected by the CO+H₂ treatment. The Fe²⁺ ions located only in tetrahedral environment were transformed into iron carbide in the X zeolite framework, while the Fe²⁺ ions of octahedral environment were also transformed in part to carbide in the ZSM-5 lattice.