Adsorption and thermal decomposition of N-methylaniline on Pt(1 1 1)

The adsorption and thermal decomposition of N-methylaniline (NMA) on the Pt(1 1 1) surface has been studied with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). NMA adsorbs molecularly at 85 K through the nitrogen lone pair and is stable up to 300 K. At temperatures of 300–350 K it converts to two or more surface intermediates including the N-methyleneaniline (NMEA) species. This NMEA intermediate dissociates upon annealing to 450 K, and further annealing leads to the desorption of HCN and H₂, leaving only C on the surface at 800 K.     

Interaction of ethylene with palladium clusters supported on oxidised tungsten foil

The reactivity with ethylene of palladium clusters supported on oxidised tungsten foil has been investigated by synchrotron radiation-induced photoelectron spectroscopy and temperature programmed desorption. The effect of the heat pre-treatment of the sample on the interaction strength with ethylene is demonstrated. Already at room temperature, adsorption of ethylene causes breaking of both the C-H and C-C bonds and the appearance of a highly reactive C₁ phase with unsaturated bonds. A part of this phase is oxidised to carbon monoxide by oxygen supplied by the support immediately after ethylene adsorption. Another part of ethylene is probably adsorbed in the form of ethylidyne. Heating at temperatures between 400 K and 500 K brings about the dissolution of the C₁ phase in the shallow subsurface region of the Pd clusters. Further oxidation of the C₁ phase by oxygen from the support proceeds at ∼600 K. Substantial reduction of the concentration of C₁ phase at room temperature is observed after heat pre-treatment of the sample at 500 K, while complete suppression of the room temperature ethylene chemisorption proceeds upon heat pre-treatment at 800 K. This effect is related to thermally induced encapsulation of palladium clusters in surface tungsten oxide.     

Glycine on Pt(111): a TDS and XPS study

The adsorption and desorption of in situ deposited glycine on Pt(111) were investigated with thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). Glycine adsorbs intact on Pt(111) at all coverages at temperatures below 250 K. The collected results suggest that the glycine molecules adsorb predominantly in the zwitterionic state both in the first monolayer and in multilayers. Upon heating, intact molecules start to desorb from multilayers around 325 K. The second (and possibly third) layer(s) are somewhat more strongly bound than the subsequent layers. The multilayer desorption follows zero order kinetics with an activation energy of 0.87 eV molecule⁻¹. From the first saturated monolayer approximately half of the molecules desorbs intact with a desorption peak at 360 K, while the other half dissociates before desorption. Below 0.25 monolayer all molecules dissociate upon heating. The dissociation reactions lead to H₂, CO₂, and H₂O desorption around 375 K and CO desorption around 450 K. This is well below the reported gas phase decomposition temperature of glycine, but well above the thermal desorption temperatures of the individual H₂, CO₂, and H₂O species on Pt(111), i.e. the dissociation is catalyzed by the surface and H₂, CO₂, and H₂O immediately desorb upon dissociation. For temperatures above 500 K the remaining residues of the dissociated molecules undergo a series of reactions leading to desorption of, for example, H₂CN, N₂ and C₂N₂, leaving only carbon left on the surface at 900 K. Comparison with previously reported studies of this system show substantial agreement but also distinct differences.     

Ceria nanoformations in CO oxidation on Pt(1 1 1): Promotional effects and reversible redox behaviour

A well-defined CeO_x/Pt(1 1 1) model catalytic system has been fabricated using the self-assembling of Ce adatoms on a Pt(1 1 1) surface with a subsequent oxidation of the nucleating Ce submonolayer (0.3 ML). The resulting system of the “inverse supported catalyst” type consists of CeO_x nanoformations (2D islands of 5-15 nm size and ∼0.3 nm in height) more or less uniformly distributed over the Pt(1 1 1) surface. This CeO_x/Pt(1 1 1) system has been tested in the CO oxidation reaction where both the CO₂ production rate and the Ce oxidation state were monitored in situ. An enhanced reactivity and a remarkable shift of the bistable region of the reaction towards higher CO pressures were observed when compared to a clean Pt(1 1 1) surface. The CeO_x islands exhibit a pronounced redox behaviour that follows the hysteresis cycle of the reaction. The usefulness of such a type of the “inverse model catalyst” for studying the oxygen diffusion supply and the redox behaviour of ceria in the ceria-platinum catalysts is demonstrated.     

Formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys

The formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys were investigated by X-ray photoelectron spectroscopy (XPS) and by adsorption of CO probe molecules, which was characterized by temperature-programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The PdAg/Pd(1 1 1) surface alloys were prepared by annealing (partly) Ag film covered Pd(1 1 1) surfaces, where the Ag films were deposited at room temperature. Surface alloy formation leads to a modification of the electronic properties, evidenced by core-level shifts (CLSs) of both the Pd(3d) and Ag(3d) signal, with the extent of the CLSs depending on both initial Ag coverage and annealing temperature. The role of Ag pre-coverage and annealing temperature on surface alloy formation is elucidated. For a monolayer Ag covered Pd(1 1 1) surface, surface alloy formation starts at ∼450 K, and the resulting surface alloy is stable upon annealing at temperatures between 600 and 800 K. CO TPD and HREELS measurements demonstrate that at 120 K CO is exclusively adsorbed on Pd surface atoms/Pd sites of the bimetallic surfaces, and that the CO adsorption behavior is dominated by geometric ensemble effects, with adsorption on threefold hollow Pd₃ sites being more stable than on Pd₂ bridge sites and finally Pd₁ a-top sites.     

Photon-induced chemical vapor deposition of molybdenum on Pt(1 1 1)

Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the adsorption and photon-induced decomposition of Mo(CO)₆. Mo(CO)₆ adsorbs molecularly on a Pt(1 1 1) surface with weak interaction at 100 K and desorbs intact at 210 K without undergoing thermal decomposition. Adsorbed Mo(CO)₆ undergoes decarbonylation to form surface Mo(CO)_x (x ? 5) under irradiation of ultraviolet light. The Mo(CO)_x species can release further CO ligands to form Mo adatoms with CO desorption at 285 K. In addition, a fraction of the released CO ligands transfers onto the Pt surface and subsequently desorbs at 350-550 K. The resulting Mo layer deposited on the Pt surface is nearly free of contamination by C and O. The deposited Mo adatoms can diffuse into the bulk Pt at temperatures above 1070 K.     

Interaction of carbon monoxide and oxygen at the surface of inverse titania/Au model catalyst

Interaction of carbon monoxide and oxygen on the surface of titania/Au(1 1 1) inverse model catalyst held at 200 K has been studied by reflection absorption infrared spectroscopy. It was found that CO adsorbs on the oxide/Au perimeter interface, whereas no or very weak adsorption was observed on Au(1 1 1) or titania surface, respectively. Exposing of such species to oxygen results in their decay possibly due to carbon dioxide formation. Efficiency of this effect is higher at lower CO initial concentration which points at the importance of free surface sites for the reaction process.     

Adsorption behavior and reaction properties of NO and CO on Rh(1 1 1)

Reactions between NO and CO on Rh(1 1 1) surfaces were investigated using infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. NO adsorbed on the fcc, atop, and hcp sites in that order, whereas CO adsorbed initially on the atop sites and then on the hollow (fcc + hcp) sites. The results of experiments with NO exposure on CO-preadsorbed Rh(1 1 1) surfaces indicated that the adsorption of NO on the hcp sites was inhibited by preadsorption of CO on the atop sites, and NO adsorption on the atop and fcc sites was inhibited by CO preadsorbed on each type of site, which indicates that NO and CO competitively adsorbed on Rh(1 1 1). From a Rh(1 1 1) surface with coadsorbed NO and CO, N₂ was produced from the dissociation of fcc-NO, and CO₂ was formed by the reaction of adsorbed CO with atomic oxygen from dissociated fcc-NO. The CO₂ production increased remarkably in the presence of hollow-CO. Coverage of fcc-NO and hollow-CO on Rh(1 1 1) depended on the composition ratio of the NO/CO gas mixture, and a gas mixture with NO/CO ? 1/2 was required for the co-existence of fcc-NO and hollow-CO at 273 K.     

The chemistry of C2 perfluoroalkyl iodide on the Cu(1 1 1) single crystal surface

The thermal chemistry of perfluoroethyl iodide (C₂F₅I) adsorbed on Cu(1 1 1) has been investigated by temperature-programmed reaction/desorption (TPR/D), reflection-absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). I 4d and F 1s XPS spectra show that dissociative adsorption of C₂F₅I to form the surface-bound perfluroethyl (Cu-C₂F₅) moieties occurs at very low temperature (T < 90 K), while the C-F bond cleavage in adsorbed perfluroethyl (Cu-C₂F₅) begins at ca. 300 K. XPS and TPR/D studies further reveal that the reactions of ^βCF₃^αCF_2(ad) on Cu(1 1 1) are strongly dependent on the surface coverage. At high coverages (?0.16 L exposure), the adsorbed perfluroethyl (Cu-C₂F₅) evolves, via α-F elimination, into the surface-bound tetrafluoroethylidene moieties (CuCF-CF₃) followed by a dimerization step to form octafluoro-2-butene (CF₃CFCFCF₃) at 315 K as gas product. The surface-bound (Cu-C₂F₅) decomposes preferentially, at low coverages (?0.04 L), via consecutive α-F abstraction to afford intermediate, trifluoroethylidyne (CuCCF₃), resulting in the final coupling reaction to yield hexafluoro-2-butyne (CF₃CCCF₃) at 425 K. However, at middle coverages (ca. 0.08-0.16 L exposure), the adsorbed perfluroethyl (Cu-C₂F₅) first experiences an α-F elimination and then prefers to loss the second F from β position to yield the intermediate of Cu-CF₂-CFCu (μ-η,η-perfluorovinyl), which may further evolve into hexafluorocyclobutene (CF₂CFCFCF₂) at 350 K through cyclodimerization reaction. Our results have also shown that the surface reactions to yield the products, CF₃CFCFCF₃ and CF₃CCCF₃, obey first-order kinetics, whereas the formation of CF₂CFCFCF₂ follows second-order kinetics.     

Collision-induced migration of CO on Pt(9 9 7) surface

Lateral displacement of adsorbates induced by collisions with energy-controlled rare gas atoms was examined in an ultra high vacuum chamber using Fourier-transform infrared (FTIR) spectroscopy and a supersonic molecular beam apparatus. A stepped Pt(9 9 7) surface was exposed to CO molecules and subsequently to energy-controlled Ne or Ar atoms. There was no change in the CO stretching mode region of the FTIR spectrum of the Pt(9 9 7) surface after Ne atoms having an average translational energy of 0.23 eV were collided with it. However, when Ne atoms having an average translational energy of 0.56 eV were collided with the surface, the intensity of the peak assigned to the CO stretching mode at terrace sites decreased, while that at step sites increased with increasing the exposure to the Ne atoms. This is the demonstration of collision-induced migration, showing that CO molecules adsorbed at the terrace sites migrate laterally to the step sites upon collision with high-energy Ne atoms. In addition, the experimental results demonstrate the existence of an additional energy barrier for jumps across the steps. This investigation demonstrates an advantage of using a molecular beam for studying adsorbate migration.     

Oxygen exchange between NO gas and adsorbed atomic oxygen on Pt(335)

We have used temperature-programmed desorption with isotopically labeled gases to study O exchange between gas phase NO and adsorbed atomic O on Pt(335). We find two distinct types of adsorbed O, one of which exchanges at least 40 times faster than the other, at room temperature. Based on their relative concentrations, we tentatively identify the more active species as O at the step edge and the less active one as O at terrace sites. The temperature dependence of the faster exchange rate implies two parallel reaction pathways. Above 240 K, the exchange rate increases with temperature with an apparent activation energy of 3.8 kcal mol⁻¹. At lower temperatures the exchange rate is nearly temperature-independent, with an apparent activation energy near zero but a very low pre-exponential factor. These results are interpreted in terms of a competition between oxygen exchange and NO desorption. The low-temperature process probably requires special sites or adsorbate configurations. The room temperature exchange rates of O₂ gas with preadsorbed atomic O, and with NO at edge sites, are more than 100 times slower than for NO gas and adsorbed O.     

High-pressure study on the adsorption and oxidation of CO on gold/titania model catalysts

The results of an IR study on the interaction of CO/O₂ gas mixtures with planar Au/TiO₂ model catalysts at elevated pressures and at room temperature are presented. The model catalysts were prepared by deposition of a flat titania film on a Ru(0 0 0 1) substrate and subsequent evaporation of gold on the titania film. In the presence of the gas mixtures, an IR band in the CO stretching region was formed, pointing to linearly adsorbed CO. The position of this band is nearly independent of the Au coverage employed. Compared to pure CO, the IR band is shifted to higher wave numbers when CO/O₂ gas mixtures are used. Although the production of CO₂ was detected in the CO oxidation reaction on the model catalysts, the formation of other IR bands, revealing the build-up of carbonates or other side-products which is usually observed for Au/TiO₂ real powder catalysts, was very weak.     

Interaction of NO with CO on Pd(100): ordered coadsorption structures and explosive reaction

An ordered mixed structure of c(3 × 2) is formed for a (NO + CO) coadsorption layer. The c(3 × 2) islands are considered to consist of equimolar NO and CO. The local fractional coverage (θ_NO + θ_CO) in the domain is estimated to be 0.33. Explosive production of CO₂ takes place in the c(3 × 2) islands. The vacancy requirement model is considered to be valid for the autocatalytic reaction. Since the reaction is not accompanied with any substrate reconstruction, the autocatalytic behaviour is attributed only to the formation of mixed islands. The desorption of N₂ follows, however, the second-order kinetics on Pd(100). As a result of the competition between NO and CO for the surface electrons, the CO-metal bond is weakened by the coadsorbed NO, which influences the explosive reaction. On the other hand, strengthening of the NO-metal bond is observed. When NO is in excess of CO, a p(3 × 2) structure coexists with the c(3 × 2) structure. The local coverage in the p(3 × 2) islands is estimated to be 0.33. In this coverage region, another path for the CO₂ production is available.     

Comparative study of photochemistry of methane on Pt(111) and Pd(111) surfaces

Adsorption states and photochemistry of methane physisorbed on Pd(111) have been investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy and compared with those on Pt(111). On both of the surfaces, methane is either dissociated into a hydrogen atom and a methyl radical or molecularly desorbed by 6.4 eV photon irradiation. In the photochemistry, the direct electronic excitation of the adsorbate-substrate complex plays an important role. Different features observed for Pd(111) compared with Pt(111) are: (1) the adsorbate-substrate interaction is slightly stronger; (2) methane adsorbates show a (√3√3)R30° LEED pattern at 40 K; (3) the photochemical cross-section is larger by 60%; and (4) the photochemistry is not self-quenched at prolonged irradiation. The origins of these features are discussed in terms of the differences in the electronic structure between the two surfaces.     

CO adsorption on the Pt(1 1 1) surface: a comparison of a gradient corrected functional and a hybrid functional

The adsorption of CO on the Pt(1 1 1) surface in a pattern has been studied with the gradient corrected functional of Perdew and Wang and the B3LYP hybrid functional. A slab which is periodic in two dimensions is used to model the system. The Perdew-Wang functional incorrectly gives the fcc site as the most favorable adsorption site, in accord with a set of previous studies. The B3LYP functional gives the top site as the preferred site. This confirms results from cluster studies where it was suggested that the different splitting, dependent on the functional, between highest occupied and lowest unoccupied molecular orbital, could be the reason for this change of the adsorption site. This is supported by an analysis based on the projected density of states and the Mulliken population.     

Probing the interactions of Pt, Rh and bimetallic Pt-Rh clusters with the TiO2(1 1 0) support

Pt, Rh, and Pt-Rh clusters on TiO₂(1 1 0) have been investigated by scanning tunneling microscopy (STM), soft X-ray photoelectron spectroscopy (sXPS), and low energy ion scattering (LEIS). The surface compositions of Pt-Rh clusters are Pt-rich (66-80% Pt) for room temperature deposition of both 2 ML of Pt on 2 ML of Rh (Rh + Pt) and 2 ML of Rh on 2 ML of Pt (Pt + Rh). Pt and Rh atoms readily diffuse within the clusters at room temperature, and although diffusion is slower at 240 K, intermixing of Pt and Rh still occurs. The binding energies of surface and bulk states for Rh(3d_5/2) and Pt(4f_7/2) can be distinguished in sXPS studies, and an analysis of these spectra indicates that the surface compositions of the Pt + Rh and Rh + Pt clusters are similar at room temperature but not identical. In addition to sintering, the pure Pt, pure Rh and Pt-Rh clusters become completely encapsulated by titania upon heating to 700 K. sXPS investigations show that annealing the clusters to 850 K induces reduction of titania support to Ti⁺² and Ti⁺³, with the extent of reduction being the greatest for Pt, the least for Rh and intermediate for Pt-Rh. We propose that TiO₂ is reduced at the metal-titania interface on top of the clusters, not at the base of the clusters. Furthermore, the extent of titania reduction is greater for metal clusters with weaker metal-oxygen bonds because oxygen atoms are less likely to migrate to the top of the clusters, and therefore the encapsulating titania is oxygen-deficient.     

Coadsorption of CO and C6H6 on Co(0 0 0 1)

We have studied the influence of CO on the adsorption of benzene on the Co(0 0 0 1) surface using LEED, XPS, TDS and work function measurements. CO was found to reduce the benzene adsorption, but even at saturation CO exposure no complete blocking was observed. Thermal desorption of the coadsorbed layer featured CO and H₂ peaks indicating partial dehydrogenation of benzene and retaining of the CO bond. Ordered LEED structures were found with all coverages: Pre-adsorption of CO led to patterns already seen for pure carbon monoxide adsorption. Pre-adsorption of benzene showed the known structure of pure benzene also with small CO exposures, but higher CO exposures yielded a mixture of and patterns.     

The temperature dependence of the interaction of NO + CO on Pt{1 0 0}

Infrared reflection absorption spectroscopy together with mass spectrometry has been used to investigate the interaction of NO and CO on Pt{1 0 0}, initially prepared in the reconstructed ‘hex’ phase, under ambient pressures of these gases, in the temperature range 300-500 K. The results allow the local and total coverages of adsorbed CO and NO to be related to the rate of reaction to produce gas phase CO₂, and provide insight into the species present on the surface during the so-called low temperature oscillatory reaction regime of this process. At temperatures below that at which NO dissociation occurs (approximately 390-400 K) adsorption is controlled by the non-reactive displacement of NO by CO and results in a CO-poisoned surface. Above 400 K when significant CO₂ production occurs, the NO coverage increases to produce a surface with NO and CO fully intermixed; the increase in NO coverage is attributed to the higher rate of NO arrival from the gas phase (with a partial pressure ratio of P_NO:P_CO>1) at free surface sites created by NO dissociation and subsequent reaction with CO. The competition between these two processes of non-reactive NO displacement by CO and reactive displacement of CO by NO is proposed to determine the parameter space of the low temperature oscillatory regime. Rapid equilibration between bridged and atop CO species leads to them appearing to exhibit identical reaction behaviour. Particularly at the lowest reaction temperatures (around 400 K), islands of pure CO may coexist on the surface but not participate in the reaction. Under conditions corresponding to the high temperature oscillatory regime, small quantities of absorbed CO, but no NO, are seen on the surface.     

Comparison of the interaction of Pd with positively and negatively poled LiNbO3(0 0 0 1)

To investigate the possibility of manipulating the surface chemical properties of finely dispersed metal films through ferroelectric polarization, the interaction of palladium with oppositely poled LiNbO₃(0 0 0 1) substrates was characterized. Low energy ion scattering indicated that the Pd tended to form three-dimensional clusters on both positively and negatively poled substrates even at the lowest coverages. X-ray photoelectron spectroscopy (XPS) showed an upward shift in the binding energy of the Pd 3d core levels of 0.9 eV at the lowest Pd coverages, which slowly decayed toward the bulk value with increasing Pd coverage. These shifts were independent of the poling direction of the substrate and similar to those attributed to cluster size effects on inert supports. Thus, the spectroscopic data suggested that Pd does not interact strongly with LiNbO₃ surfaces. The surface chemical properties of the Pd clusters were investigated using CO temperature programmed desorption. On both positively and negatively poled substrates, CO desorption from freshly deposited Pd showed a splitting of the broad 460 K desorption peak characteristic of bulk Pd into distinct peaks at 270 and 490 K as the Pd coverage was decreased below 1.0 ML; behavior that also resembles that seen on inert supports. It was found that a small fraction of the adsorbed CO may dissociate (<2%) for Pd on both positively and negatively poled substrates. The thermal response of the smaller Pd clusters on the LiNbO₃ surfaces, however, was different from that of inert substrates. In a manner similar to Nb₂O₅, when CO desorption experiments were carried out a second time, the adsorption capacity decreased and the higher temperature desorption peak shifted from 490 K to below 450 K. This behavior was independent of the substrate poling direction. Thus, while there was evidence that LiNbO₃ does not behave as a completely inert support, no significant differences between positively and negatively poled surfaces were observed. This lack of sensitivity of the surface properties of the Pd to the poling direction of the substrate is attributed to the three-dimensional Pd clusters being too thick for their surfaces to be influenced by the polarization of the underlying substrate.