Hydrogen adsorption and diffusion on Pd(1 1 1)

The adsorption, diffusion and ordering of hydrogen on Pd(1 1 1) was studied by scanning tunneling microscopy in the temperature range of 37-90 K. At low coverage isolated hydrogen atoms were observed. They formed √3×√3-1H islands as the coverage increased. Above 1/3 monolayer (ML) coverage areas of a new phase with √3×√3-2H structure were formed, with both structures coexisting between 1/3 and 2/3 ML. Finally a 1 × 1 structure was formed after high exposures of hydrogen above 50 K, with a coverage close to 1 ML. Atomically resolved images reveal that H binds to fcc hollow sites.     

Adsorption of carbon monoxide on Pd(3 1 1) and (2 1 1) surfaces

Adsorption of carbon monoxide on Pd(3 1 1) and (2 1 1) stepped surfaces has been investigated by the extended London-Eyring-Polyani-Sato (LEPS) method constructed using a 5-parameter Morse potential. The calculated results show that there exist common characteristics of CO adsorption on the two surfaces. At low coverage, CO occupies threefold hollow site of the (1 1 1) terrace and is tilted with respect to the surface normal. Among the threefold hollow sites on the (1 1 1) terrace, the nearer the site is to the step, the greater is the influence of the step. The twofold bridge site on the (1 0 0) step is also a stable adsorption site at high coverage. Because of the different lengths of the (1 1 1) terraces, the (3 1 1) and (2 1 1) stepped surfaces have different characteristics. A number of new sites are exposed on the boundary regions, including the fourfold hollow site (H₄) of the (3 1 1) surface and the fivefold hollow site (H₅) of the (2 1 1) surface. At high coverage, CO resides in the H₅ site of the (2 1 1) surface, but the H₄ site of the (3 1 1) surface is not a stable adsorption site. This study further shows that the on-top site on the (1 0 0) step of Pd(3 1 1) is a stable adsorption site, but the same type of site on Pd(2 1 1) is not.     

Infrared reflection absorption spectral study for CO adsorption on Pd/Pt(1 1 1) bimetallic surfaces

Infrared reflection absorption spectroscopy (IRRAS) was used to investigate carbon monoxide (CO) adsorption on 0.15 nm-thick-0.6 nm-thick Pd-deposited Pt(1 1 1) bimetallic surfaces: Pd_x/Pt(1 1 1) (where x is the Pd thickness in nanometers) fabricated using molecular beam epitaxial method at substrate temperatures of 343 K, 473 K, and 673 K. Reflection high-energy electron diffraction (RHEED) measurements for Pd_0.15-0.6 nm/Pt(1 1 1) surfaces fabricated at 343 K showed that Pd grows epitaxially on a clean Pt(1 1 1), having an almost identical lattice constant of Pt(1 1 1). The 1.0 L CO exposure to the clean Pt(1 1 1) at room temperature yielded linearly bonded and bridge-bonded CO-Pt bands at 2093 and 1855 cm⁻¹. The CO-Pt band intensities for the CO-exposed Pd_x/Pt(1 1 1) surfaces decreased with increasing Pd thickness. For Pd_0.3 nm/Pt(1 1 1) deposited at 343 K, the 1933 cm⁻¹ band caused by bridge-bonded CO-Pd enhanced the spectral intensity. The linear-bonded CO-Pt band (2090 cm⁻¹) almost disappeared and the bridge-bonded CO-Pd band dominated the spectra for Pd_0.6 nm/Pt(1 1 1). With increasing substrate temperature during the Pd depositions, the relative band intensities of the CO-Pt/CO-Pd increased. For the Pd_0.3 nm/Pt(1 1 1) deposited at 673 K, the linear-bonded CO-Pt and bridge-bonded CO-Pd bands are located respectively at 2071 and 1928 cm⁻¹. The temperature-programmed desorption (TPD) spectrum for the 673 K-deposited Pd_0.3 nm/Pt(1 1 1) showed that a desorption signal for the adsorbed CO on the Pt sites decreased in intensity and shifted ca. 20 K to a lower temperature than those for the clean Pt(1 1 1). We discuss the CO adsorption behavior on well-defined Pd-deposited Pt(1 1 1) bimetallic surfaces.     

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.     

Growth of epitaxial thin Pd(1 1 1) films on Pt(1 1 1) and oxygen-terminated FeO(1 1 1) surfaces

Thin Pd films (1-10 monolayers, ML) were deposited at 35 K on a Pt(1 1 1) single crystal and on an oxygen-terminated FeO(1 1 1) monolayer supported on Pt(1 1 1). Low energy electron diffraction, Auger electron spectroscopy, and Kr and CO temperature programmed desorption techniques were used to investigate the annealing induced changes in the film surface morphology. For growth on Pt(1 1 1), the films order upon annealing to 500 K and form epitaxial Pd(1 1 1). Further annealing above 900 K results in Pd diffusion into the Pt(1 1 1) bulk and Pt-Pd alloy formation. Chemisorption of CO shows that even the first ordered monolayer of Pd on Pt(1 1 1) has adsorption properties identical to bulk Pd(1 1 1). Similar experiments conducted on FeO(1 1 1) indicate that 500 K annealing of a 10 ML thick Pd deposit also yields ordered Pd(1 1 1). In contrast, annealing of 1 and 3 ML thick Pd films did not result in formation of continuous Pd(1 1 1). We speculate that for these thinner films Pd diffuses underneath the FeO(1 1 1).     

RAIRS studies of CO adsorption on Pd/CeO2−x(1 1 1)/Pt(1 1 1)

Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO_2−x-supported Pd nanoparticles at room temperature. The results show that when CeO_2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO_2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO_2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO_2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO_2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.     

Methanol adsorption on Pd(1 1 0) and Ag/Pd(1 1 0) studied by high-resolution photoelectron spectroscopy

Adsorption of methanol on clean Pd(1 1 0) and on an alloyed Ag/Pd(1 1 0) surface has been studied by high-resolution photoelectron spectroscopy. On Pd(1 1 0) two different chemisorbed methanol species were observed for temperatures up to 200 K, with the one at lower binding energy remaining at low coverage. These species were attributed to methanol adsorbed in two different adsorption sites on the Pd(1 1 0) surface. As is well established for this system, heating to 250 K resulted in decomposition of methanol into CO. The adsorption and decomposition behaviour of methanol on the Ag/Pd(1 1 0) surface alloy formed by depositing Ag on Pd(1 1 0) at elevated temperature was similar to that of the pure Pd(1 1 0) surface. This suggests that the amount of Ag present in the Pd(1 1 0) surface in this study does not affect the decomposition behaviour of methanol as compared to pure Pd(1 1 0). Complementary density functional theory calculations also show little influence of Ag on the binding of methanol to Pd. These calculations predict an on-top adsorption site for low methanol coverages.     

Deactivation of Pd particles supported on Nb2O5/Cu3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

Structural changes that occur on Pd-Nb₂O₅/Cu₃Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb₂O₅ over Pd particles to cause the observed effect and rather suggests the formation of “mixed Pd-NbO_x” sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of “mixed Pd-NbO_x” sites in catalytic reactions.     

Surface structures of atomic hydrogen adsorbed on Cu(1 1 1) surface studied by density-functional-theory calculations

The surface structures of atomic hydrogen adsorbed on Cu(1 1 1) surface have been studied theoretically by using density-functional-theory calculations. The results show that 0.67 ML hydrogen adsorbed on threefold hollow sites forming (3 × 1) superstructure and 0.5 ML hydrogen adsorbed on threefold hollow sites forming (2 × 2)-2H superstructure with central H at trigonal sites induce most significant substrate reconstructions and that fits best the observed (3 × 3) and (2 × 2) LEED patterns, respectively. The potential energies for the hydrogen in these two models are also lower than those in other competing models. Accordingly, these two models are the most preferable structures for 0.5-0.67 ML and 0.3-0.5 ML hydrogen adsorbed on the Cu(1 1 1) surface. In addition, the calculations also suggest that the lateral H-H interaction is not of simple repulsion and how the adsorbed hydrogen is arrayed is important in modifying the adsorption energy.     

The dissimilar twins - a comparative, site-selective in situ study of CO adsorption and desorption on Pt(3 2 2) and Pt(3 5 5)

The adsorption and desorption of CO on stepped Pt(3 2 2) = Pt(S)-[5(1 1 1) × (1 0 0)] and Pt(3 5 5) = Pt(S)-[5(1 1 1) × (1 1 1)] were investigated using in situ high-resolution X-ray photoelectron spectroscopy at BESSY II, which allows to clearly distinguish between different step and terrace adsorption sites. For the two surfaces, with the same nominal terrace width of five atomic rows, but different step orientation, significant differences are observed. While for Pt(3 5 5) CO adsorption at steps only occurs at on-top sites, on Pt(3 2 2) both step on-top and bridge sites are occupied, albeit with a significantly lower coverage (0.07 vs. 0.13 ML at 200 K). On both surfaces terrace sites are only occupied when the step sites are almost saturated confirming the enhanced binding energy at step sites. CO adsorbed at the (1 1 1) steps on Pt(3 5 5) is more strongly bound than on the (1 0 0) steps on Pt(3 2 2), which is attributed to the different electronic and geometric structure of the steps. The relative occupation of terrace and step sites at a given coverage remains the same between 120 and 290 K on Pt(3 5 5) K, but shows major changes on Pt(3 2 2), between step on-top and bridge sites as well as terrace on-top and bridge sites. On Pt(3 5 5) a smaller CO terrace coverage is found (0.36 vs. 0.40 ML on Pt(3 2 2) at 200 K), mainly due to the lower occupation of terrace bridge sites. For Pt(3 2 2), an ordered adsorbate phase is deduced from a c(4 × 2)-like LEED pattern, which indicates adsorbate order beyond the extension of a single terrace. A model for this structure is proposed.     

Quantum states of hydrogen (H, D, T) atoms on Cu(1 0 0) and (1 1 0) surfaces

We investigate the quantum mechanical behavior of adsorbed hydrogen (H, D, T) on Cu(1 0 0) and (1 1 0) surfaces. We construct potential energy surfaces (PESs) for the motion of the hydrogen H atom on Cu(1 0 0) and (1 1 0) surfaces within the framework of density functional theory. The potential energy takes a minimum value on the hollow site of Cu(1 0 0) and on the short bridge site of Cu(1 1 0). Moreover, we calculate the quantum states of hydrogen atom motion on these calculated PESs. The ground state wave function of the hydrogen atom motion is strongly localized around the hollow site on the Cu(1 0 0) surface. On the other hand, the ground state wave function of the hydrogen atom motion on Cu(1 1 0) is distributed from the short bridge site to two neighboring pseudo-threefold sites. We finally show isotope effects on the quantum states of the motion of hydrogen on both surfaces.     

Chemisorption of atomic oxygen on Pd(1 1 1) studied by STM

Atomic oxygen resulting from the dissociation of O₂ on Pd(1 1 1) at low coverage was studied in a variable temperature scanning tunneling microscope (STM) in the range from 30 to 210 K. Oxygen atoms, which typically appear as 30-40 pm deep depressions on Pd(1 1 1), occupy fcc hollow sites and form ordered p(2 × 2) islands upon annealing above 180 K. The mobility of the atoms diminishes rapidly below 180 K, with an approximate diffusion barrier of 0.4-0.5 eV. Oxygen atom pairs produced by thermal dissociation of O₂ at 160 K occupy both fcc and hcp hollow sites. The atoms travel approximately 0.25 nm after dissociation, and the distribution of pairs is strongly influenced by the presence of subsurface impurities within the Pd sample. At much lower temperatures, the STM tip can dissociate oxygen molecules. Dissociation occurs at sample bias voltages exceeding approximately 0.1 V. Following tip-induced dissociation, the product atoms occupy only fcc hollow sites. Oxygen atoms can be manipulated via short range repulsive interactions with the STM tip.     

Surface structure of K/Pd(1 0 0) and the effect of H coadsorption: Density functional theory calculations

We have performed density-functional theory calculations to study the atomic structure of the K/Pd(1 0 0)-p(2 × 2) and -c(2 × 2) surfaces formed at 0.25 ML and 0.5 ML, respectively. We find that K atoms prefer the hollow site with the K adsorption height 2.44 Å for p(2 × 2) and 2.50 Å c(2 × 2). The first interlayer spacing (d₁₂) of the Pd(1 0 0) substrate appears slightly contracted from the bulk value as Δd₁₂ = −0.8% and −0.3% for p(2 × 2) and c(2 × 2), respectively. The calculated contraction Δd₁₂ = −0.3% for c(2 × 2) is not in accord with the expansion Δd₁₂ = +1.3% reported by a low-energy electron diffraction (LEED) study. As the origin of this difference, a possibility of hydrogen contamination of the surface sample used in the LEED study is suggested: Our calculations show that the d₁₂ of K/Pd(1 0 0)-c(2 × 2) increases linearly with the coverage of H coadsorption, which leads to an estimation for the H coverage of the surface sample as 0.1-0.4 ML.     

Coverage-dependent absorption of atomic hydrogen into the sub-surface of Cu(1 1 1) studied by density-functional-theory calculations

With density-functional-theory calculations, we have studied coverage-dependent absorption of H atoms into the sub-surface below a face-centered-cubic (fcc) hollow site of Cu(1 1 1). Both frozen and relaxed surface lattices were considered when the atomic H migrated from the surface to the sub-surface. The potential energy curve for the absorbing H shows that the surface site is in general favored over the sub-surface site, and this trend varies little with the H coverage (0.11-0.67 ML). If the hexagonal-close-packed (hcp) hollow sites immediately vicinal to the absorbing H are pre-adsorbed with other H atoms, the surface adsorption potential is greatly increased, because of the repulsive H-H interaction, to a value near, or even greater than, the sub-surface absorption potential; when two or three H atoms (on the hcp sites) are beside the absorbing H, the energy barrier for the sub-surface absorption is decreased, whereas that for diffusion from the sub-surface to the surface is enhanced. These results indicate that, on an H-saturated Cu(1 1 1) surface (0.67 ML), the sub-surface sites below the fcc sites with two or three neighboring H atoms can trap the sub-surface H.     

Effects of predosed oxygen and hydrogen on CO adsorption on Ni(1 0 0)

We present the results of high-resolution electron energy loss experiments on (CO/O)/Ni(1 0 0) and (CO/H)/Ni(1 0 0) systems. Oxygen and hydrogen interact differently with Ni(1 0 0) surface, nevertheless, both species do not affect to a great extent the vibrational properties of CO. A phase of CO molecules weakly bonded to the surface and unaffected by coadsorbed oxygen and hydrogen, is found. Coverage of 0.5 ML of predosed oxygen chemically passivates the Ni(1 0 0) surface and inhibits any CO adsorption at room temperature. CO sites are unambiguously determined for each predosed Ni(1 0 0) 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.     

Adsorption site, core level shifts and charge transfer on the Pd(1 1 1)-I(√3 × √3) surface

We use core level photoelectron spectroscopy and density functional theory (DFT) to investigate the iodine-induced Pd(1 1 1)-I(√3 × √3) structure formed at 1/3 ML coverage. From the calculations we find that iodine adsorbs preferentially in the fcc hollow site. The calculated equilibrium distance is 2.06 Å and the adsorption energy is 68 kcal/mol, compared to 2.45 Å and 54 kcal/mol in the atop position. The adsorption energy difference between fcc and hcp hollows is 1.7 kcal/mol. Calculated Pd 3d surface core level shift on clean Pd(1 l 1) is 0.30 eV to lower binding energy, in excellent agreement with our experimental findings (0.28-0.29 eV). On the Pd(1 1 1)-I(√3 × √3) we find no Pd 3d surface core level shift, neither experimentally nor theoretically. Calculated charge transfer for the fcc site, determined from the Hirshfeld partitioning method, suggests that the iodine atom remains almost neutral upon adsorption.     

Adsorption of carbon monoxide Au/Pd(1 0 0) alloys in ultrahigh vacuum: Identification of adsorption sites

The adsorption of carbon monoxide is studied on Au/Pd(1 0 0) alloys by means of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The alloy was formed by adsorbing a four-monolayer thick gold film on a Pd(1 0 0) substrate and by heating to various temperatures to form alloys with a range of palladium coverages. The alloy was characterized using X-ray photoelectron spectroscopy and the composition of the outermost layer measured using low-energy ion scattering spectroscopy. CO adsorbs on palladium bridge sites only for palladium coverages greater than 0.5 monolayers (ML) suggesting that next-nearest neighbor sites are preferentially populated by palladium atoms. CO adsorbs on atop palladium sites and desorbs at ∼350 K corresponding to a desorption activation energy of ∼117 kJ/mol. However, at lower palladium coverages, these sites are not occupied and CO desorption states are detected 170 and 112 K corresponding to desorption activation energies of ∼53 kJ/mol and ∼35 kJ/mol, respectively, for these states. It is suggested that these states are due to a restructuring of the surface to form low-coordination gold sites that obscure the atop palladium site.     

Electronic properties of thin Zn layers on Pd(1 1 1) during growth and alloying

The growth and alloying of thin Zn layers on Pd(1 1 1) was investigated using X-ray and ultraviolet photoelectron spectroscopy as well as low energy electron diffraction and correlated with density functional calculations. At 105 K, the formation of a pseudomorphic Zn monolayer is observed. Upon heating this layer to 550 K or upon deposition of 1 ML at 550 K, an ordered p(2 × 1) PdZn surface alloy with a Pd:Zn ratio of ∼1:1 is formed, with a characteristic Pd 3d_5/2 peak at a binding energy of ∼335.6 eV. For deposition of 3 ML Zn at 550 K or by heating 3 ML, deposited at low temperature, to 500 or 600 K, a PdZn alloy with a Pd:Zn ratio of again ∼1:1 is found in the surface region, with a Pd 3d_5/2 peak at ∼335.9 eV; the direct preparation at 550 K leads to a more homogeneous and better ordered alloy. The valence band spectrum of this alloy with a low density of states at the Fermi level and pronounced maxima due to the “Pd 4d” band at ∼2.4 and 3.9 eV closely resembles the spectrum of Cu(1 1 1), in good agreement with the calculated density of states for a PdZn alloy of 1:1 stoichiometry. The shift of the “Pd 4d” band to higher binding energies as compared to Pd(1 1 1) indicates a charge transfer from Zn to the Pd 4d levels. Overall, the similarity between the ultraviolet photoelectron spectra for the PdZn alloy and for Cu(1 1 1) is taken as explanation for the similar chemical activity of both systems in methanol steam reforming.     

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.