A comparative analysis of electron spectroscopy and first-principles studies on Cu(Pd) adsorption on MgO

Ultrathin MgO films were grown on a W(1 1 0) substrate while metastable impact electron (MIES) and photoelectron (UPS) spectra were measured in situ; apart from the valence band emission, no additional spectral features were detected. The oxide surface was exposed to metal atoms (Cu, Pd) at RT. A comparison with the DOS extracted from first-principles DFT calculations shows that the metal-induced intensity developing above the top of the O 2p valence band in the UP spectra under Cu(Pd) exposure is caused by Cu 3d (Pd 4d) emission. The emission seen in the MIES spectra is attributed to the ionization of Cu 3d and 4s states of adsorbed neutral Cu atoms in an Auger process, Auger neutralization, involving two electrons from the surface, at least one of them from the metal adsorbate. The shape of the MIES spectra suggests metallic island growth even at the lowest studied exposures, which is supported by the first-principles calculations.     

The adsorption of oxygen and water on Ca and CaO films studied with MIES, UPS and XPS

Metastable induced electron spectroscopy (MIES), Ultraviolet photoelectron spectroscopy (UPS), and X-ray photoelectron spectroscopy (XPS) are employed to study the adsorption of water on Ca and CaO films as well as the adsorption of oxygen on Ca films. Ca films are prepared by evaporation of Ca onto clean Si(1 0 0) substrates. CaO films are produced by Ca evaporation in an oxygen atmosphere at a substrate temperature of 400 °C. Gas adsorption on the Ca films at room temperature, both for oxygen and water, is initiated by complete dissociation of the impinging molecules leading to the formation of Ca–O bonds. Exposure to water furthermore leads to the formation of hydroxyl groups via hydrogen abstraction from water forming a complete surface layer. Hydroxyl groups are also formed upon exposure of CaO films to water, but to a significantly smaller amount compared to Ca films exposed to water.     

Identification of Cu(I) and Cu(II) oxides by electron spectroscopic methods: AES,ELS and UPS investigations

The externally prepared black-coloured copper oxide (T? 700 K, P_O2 ? 100 torr) on a Cu(100) surface is identified by electron spectroscopy as CuO. Compared to the red-coloured Cu(I) oxide (in situ oxidation at T ? 400 K, P_O2 ? 0.5 torr, ～ 10⁹ L), the He(I)- excited photoemisson from CuO reveals characteristic shake-up satellites 10–12 eV below E_F and a broadened emission from overlapping oxygen-induced 2p and Cu 3d states. From the AES and ELS results, in correlation with the data from core electron spectroscopy, chemical shifts of Cu 2p, Cu 3s and Cu 3p in CuO to higher binding energy and decreases in binding energy of the oxygen-induced states were deduced. The unoccupied electron states of Cu at 5 and 7.5 eV above E_F — postulated from the ELS results — are preserved in Cu₂O and CuO compounds. Annealing of the Cu(II) oxide at 670 K is accompanied by decomposition into Cu₂O due to the solid-state reaction following the scheme: 2CuO → 1/2 O₂ + Cu₂O.     

Corrosion of aluminium components studied with MIES, UPS and XPS

We use X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable impact electron spectroscopy (MIES) to investigate the corrosion of aluminium components. Clean aluminium films were prepared under ultrahigh vacuum (UHV) conditions and exposed to water and NaCl. We attempt to provide a model for the mechanism of this interaction and its effects on the durability of the components.     

XPS,UPS and thermal desorption studies of alcohol adsorption on Cu(110): I. Methanol

The adsorption of methanol on clean and oxygen dosed Cu(110) surfaces has been studied using temperature programmed reaction spectroscopy (TPRS), ultra-violet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). Methanol was adsorbed on the clean surface at 140 K in monolayer quantities and subsequently desorbed over a broad range of temperature from 140 to 400 K. The UPS He (II) spectra showed the 5 highest lying emissions seen in the gas phase spectrum of methanol with a chemisorption bonding shift of the two highest lying orbitais due to bonding to the surface via the oxygen atom with which these orbitals are primarily associated. A species of quite a different nature was produced by heating this layer to 270 K. Most noticeably the UPS spectrum showed only 3 emissions and the maximum coverage of this state was approximately $\text{1}\text{2}$ monolayer. The data are indicative of the formation of a methoxy species, thus showing that methanol is dissociated on the clean Cu(110) surface at 270 K. The same dissociated species was observed on the oxygen dosed surface, the main difference in this ease being the production of large amounts of H₂CO observed in TPRS at 370 K.     

XPS,UPS and thermal desorption studies of alcohol adsorption on Cu(110): II. Higher alcohols

Preceding work dealing with the adsorption of methanol on Cu(110) has been extended to include ethanol, n- and iso-propanol and a diol, ethylene glycol. In common with the simplest alcohol, all these molecules are able to form a stable alkoxy species on the surface, that is, the alcohol dissociated at the O-H group. However, in contrast to methanol on the clean surface for which the dissociated methoxy and hydrogen recombined to desorb as methanol, all the higher alcohols reacted further with the surface, dehydrogenating to yield the corresponding aldehyde or ketone in the gas phase. Ethylene glycol reacted to form the most strongly bound intermediate of all, decomposing near 390 K to produce the dialdehyde, glyoxal, with little evidence of monoaldehyde formation or C-C bond breakage. The influence of pre-adsorbed oxygen on these reactions was to generally increase the amount of alkoxy formed on the surface by enhancing the amount of dissociative adsorption (water is formed by the deprotonation of adsorbed alcohol molecules by oxygen atoms). The alkoxide decomposition peaks were shifted to slightly higher temperatures and considerably broadened in such experiments. The decomposition peak temperatures of the different surface alkoxides correlate fairly well with literature values of the αC-H bond strength, which is weaker in iso-propanol than in methanol. XPS showed broad O(1s) spectra for all the molecules adsorbed at 140 K, probably due to hydrogen-bonding effects in the adlayer, with peak emissions at around 533 eV. When the surface was warmed to 250 K, the O(1s) spectra narrowed to close to instrumental linewidths with a concomitant shift to a lower binding energy near 531 eV. C(1s) spectra showed little change between the adsorbed alcohol and alkoxy species. The UPS showed low temperature spectra similar to the gas phase, but the highest occupied orbitals, which are essentially O(2p) orbitals, showed a chemisorption bonding shift of several tenths of an electron volt. UPS for these molecules is shown to have considerable less utility than for the simplest molecule, methanol, due to the masking of possible orbital shifts during chemical changes on the surface by the presence of overlapping emissions in the spectra.     

The adsorption of CO2 and CO on Ca and CaO films studied with MIES, UPS and XPS

Metastable Induced Electron Spectroscopy (MIES), Ultraviolet Photoelectron Spectroscopy (UPS), and X-ray Photoelectron Spectroscopy (XPS) are employed to study the adsorption of CO₂ and CO on Ca and CaO films. Ca films are prepared by evaporation of Ca onto clean Si(1 0 0) substrates. CaO films are produced by Ca evaporation in an oxygen atmosphere at a substrate temperature of 670 K. CO₂ interaction with the Ca films is initiated by dissociation of the impinging molecules leading to the formation of Ca-O bonds. These Ca-O bonds are subsequently consumed in the formation of a closed CaCO₃ layer on top of the surface. CO interaction with the Ca surfaces also leads to the dissociation of the molecule and the formation of Ca-O bonds. We find evidence for the subsequent formation of complexes on top of the surface. On CaO surfaces, both CO₂ and CO lead to the formation of a closed CaCO₃ top layer, though displaying very different reaction rates.     

CO adsorption on Ni, Pd, Cu and Ag deposited on MgO, CaO, SrO and BaO: Density functional calculations

The adsorption properties of CO molecules adsorbed on Ni, Pd, Cu and Ag atoms deposited on O²⁻, F and F⁺ sites of MgO, CaO, SrO and BaO terrace surfaces have been studied by means of density functional calculations and embedded cluster model. The examined clusters were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. The adsorption properties of CO have been analyzed with reference to the basicity of the oxide support, bond order conservation energy, pairwise and non-pairwise additivity, associative adsorption, electrostatic potentials, and orbital interactions. CO adsorption on an oxide support is drastically enhanced when CO is adsorbed on a metal deposited on this support. A dramatic change is found, and explained, when one compares the CO binding energy to O²⁻ and F sites. The formation of a strong bond at the support-metal interface has a considerable consequence on the metal-CO binding energy. The binding of CO is dominated by the metal-CO pairwise additive term, and the non-additivity term increases with increasing the basicity of the support. While the classical contributions to the electrostatic interactions are quite similar for the deposited metals, they are quite dissimilar when going from defect-free to defect-containing surfaces. The adsorption properties correlate linearly with the basicity and energy gaps of the oxide support where the electrostatic potential generated by the oxide modifies the physical and chemical properties of the adsorbed metal and therefore its reactivity versus the CO adsorbate.     

Atomic and molecular adsorption on Pd(111)

The adsorption properties of a variety of atomic species (H, O, N, S, and C), molecular species (N₂, HCN, CO, NO, and NH₃) and molecular fragments (CN, NH₂, NH, CH₃, CH₂, CH, HNO, NOH, and OH) are calculated on the (111) facet of palladium using periodic self-consistent density functional theory (DFT–GGA) calculations at ¼ ML coverage. For each species, we determine the optimal binding geometry and corresponding binding energy. The vibrational frequencies of these adsorbed species are calculated and are found to be in good agreement with experimental values that have been reported in literature. From the binding energies, we calculate potential energy surfaces for the decomposition of NO, CO, N₂, NH₃, and CH₄ on Pd(111), showing that only the decomposition of NO is thermochemically preferred to its molecular desorption.     

Hydrogen adsorption on Pd(133) surface

An approach based on measurements of the total energy distribution (TED) of field emitted electrons is used in order to examine properties of the Pd(133) from the aspect of hydrogen adsorption. The most favourable sites offered to a hydrogen atom to be adsorbed are indicated and an attempt to ascribe the peaks of the enhancement factor R in the TED spectrum to the specific adsorption sites is made.      

The interaction of oxygen molecules with iron films studied with MIES,UPS and XPS

X-ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of oxygen molecules with iron films. Supplementarily, iron oxide was investigated for comparison.With XPS from the Fe 2p_3/2 range contributions of metallic Fe as well as Fe²⁺ and Fe³⁺ can be distinguished. During the interaction with oxygen an oxide film is formed on the iron surface. Nevertheless, XPS still shows metallic contributions even for a surface which is saturated with more than 10⁴ L. The oxide film hinders the dissociation of further impinging oxygen molecules.The interaction of He* atoms with iron oxide surfaces during MIES is dominated by Auger Neutralization. This surprising result follows from the high work function and the fact that intrinsic defects result in a Fermi level pinning to the conduction band.     

Atomic adsorption of oxygen on Cu(111) and Cu(110)

We have studied angle-resolved inverse photoemission ( = 9.7 eV) after room temperature adsorption of oxygen on Cu(111) and Cu(110). On Cu(111) exposure to 500 L induces a band (3.0 eV aboveE _F at) which shows clear dispersion (1.0 eV) to higher energies for off normal incidence. Since no LEED superstructure is seen for that system, our results present strong evidence for the presence of short-range surface order. Two adsorbate bands are identified (2.8 eV and 6.3 eV at) on Cu(110)p(2×1)-O. Our results are in good agreement with a long-bridge adsorption site.     

Bromine adsorption on Cu(111)

The dissociative chemisorption of molecular bromine on Cu(111) at 300 K has been studied using ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function change measurements. A (√3 × √3)R30° structure is formed initially at a bromine coverage of 0.33 ML. This then converts to a (9√3 × 9√3)R30° compression structure with a coverage of 0.41 ML. The coincidence distance of the compression structure is determined entirely by the van der Waals diameter of adsorbed bromine. The applicability of using the van der Waals diameters of the three halogens, Cl, Br and I, to predict the saturation compression structures on Cu(111), is discussed.     

Ethylene-oxide adsorption on Ni(111): Hreels and Arups investigations

The adsorption of ethylene-oxide (Et-O) on Ni(111) was studied with high resolution electron energy loss spectroscopy and angular resolved UV-light induced photoelectron spectroscopy (ARUPS) at 140K; these measurements were complemented by thermal desorption spectroscopy (TDS) and workfunction change measurements ( δφ ).For fractional Et-O monolayer coverages five loss peaks were observed with HREELS at 835, 1155, 1270, 1495 and 3150 cm⁻¹ which are attributed to the C₂O ring deformation, CH₂ wagging and twisting modes, to the C₂O ring breathing, to the CH₂ scissor modes and C-H stretching modes of molecular adsorbed Et-O. At low coverage, the HREELS is dominated by the 835 and 3150 cm⁻¹ losses, whereas the 1155, 1270 and 1495 cm⁻¹show only weak intensities. The latter loss peaks increase significantly in intensity for Et-O coverage near the saturation of the first adsorption layer, θ (Et-O)~0.3.UPS measurements confirm the molecular adsorption of Et-O on Ni(111) at 140 K. Compared to the Et-O gas phase UPS, a considerable shift to lower binding energy is observed for the 6a₁ oxygen lone pair orbital and also for the 2b₁ (n, σ_CO, σ_CC) which has some lone pair character. These chemical shifts suggest a bonding of Et-O to Ni(111) through the oxygen atom.     

Oxygen adsorption on stepped Pd(100) surfaces

We use scanning tunneling microscopy (STM) and high-resolution core-level spectroscopy (XPS) measurements to study the initial oxidation of vicinal Pd(100) surfaces exhibiting close-packed (111) steps. The XPS data analysis is supported by detailed surface-core level shift calculations based on density-functional theory. Both STM images and the XPS spectra are found to be perfectly consistent with a characteristic zigzag O decoration of the Pd steps predicted by a preceding cluster-expansion based theoretical study [Y. Zhang and K. Reuter, Chem. Phys. Lett. 465, 303 (2008)]. Continued oxygen uptake leads to the additional stabilization of a p(2 × 2)-O overlayer on the Pd(100) terraces, and ultimately to step bunching with the resulting large Pd(100) terraces covered by the PdO(101) surface oxide.     

Oxygen adsorption on a Pd(111) surface

The interaction of oxygen with Pd(111) has been studied by means of AES, ELS, thermal desorption (TD), electron stimulated desorption (ESD) and work function measurements. It was found that a very small part ( ～ 2–3%) of the available adsorption sites are contributing to the O⁺ electron stimulated yield, the population of the latter being accompanied by enormously large work function changes (up to ～ 0.9 eV). A mechanism of adsorption and depopulation of these sites involving oxygen bulk and surface diffusion has been proposed.     

Infrared reflection absorption study of carbon monoxide adsorption on Pd/Cu(1 1 1)

Pd-Cu bimetallic surfaces formed through a vacuum-deposition of Pd on Cu(1 1 1) have been discussed on the basis of carbon monoxide (CO) adsorption: CO is used as a surface probe and infrared reflection absorption (IRRAS) spectra are recorded for the CO-adsorbed surfaces. Low energy electron diffraction (LEED) patterns for the bimetallic surfaces reveal six-fold symmetry even after the deposition of 0.6 nm. The lattice spacings estimated by the separations of reflection high-energy electron diffraction (RHEED) streaks increase with increasing Pd thickness. Room-temperature CO exposures to the bimetallic surfaces formed by the Pd depositions less than 0.3 nm thickness generate the IRRAS bands due to the three-fold-hollow-, bridge- and linear-bonded CO to Pd atoms. In particular, on the 0.1 nm-thick Pd surface, the linear-bonded CO band becomes apparent at an earlier stage of the exposure. In contrast, the bridge-bonded CO band dominates the IRRAS spectra for CO adsorption on the 0.6 nm-thick Pd surface, at which the lattice spacing corresponds to that of Pd(1 1 1). A 90 K-CO exposure to the 0.1 nm-thick Pd surface leads to the IRRAS bands caused not only by CO-Pd but also by CO-Cu, while the Cu-related band is almost absent from the spectra for the 0.3 nm-thick Pd surface. The results clearly reveal that local atomic structures of the outermost bimetallic surface can be discussed by the IRRAS spectra for the probe molecule.     

Comparison of the CO and D2 oxidation reactions on Pd supported on MgO(100), MgO(110) and MgO(111)

Oxidation of D₂ and CO on oxygen pre-exposed 200 nm thick Pd films, epitaxially grown on MgO(100), MgO(110) and MgO(111), has been investigated in the temperature range 100–300°C. Oxygen initial sticking coefficients have been determined to be close to 1 for the 100 and 110 films, and around 0.8 for the 111 film. The sticking coefficient and reactive sticking coefficient for CO oxidation on Pd/MgO(100) is also close to 1, and the maximum reactive sticking coefficient for hydrogen oxidation is determined to be around 0.9 at temperatures above 200°C. It is shown that the reactivities for the different surfaces vary strongly with surface and oxygen coverage, and the consequence of this for supported particle catalysts is pointed out.     

CO and hydrogen adsorption on Pd(2 1 0)

We have studied the adsorption of CO on Pd(2 1 0) by performing density functional theory (DFT) calculations within the generalized gradient approximation. We find a relatively small corrugation in the CO adsorption energies with the two bridge sites being energetically almost degenerate. CO is furthermore known as a strong poison in heterogeneous catalysis. We have therefore also addressed the coadsorption of CO with atomic hydrogen. There is a significant inhibition of the hydrogen adsorption due to the presence of CO which is analysed in terms of the electronic structure of the adsorbate system.