Probing the properties of the (1 1 1) and (1 0 0) surfaces of LaB6 through infrared spectroscopy of adsorbed CO

The adsorption of carbon monoxide on the LaB₆(1 0 0) and LaB₆(1 1 1) surfaces was studied experimentally with the techniques of reflection absorption infrared spectroscopy and X-ray photoelectron spectroscopy. The interaction of CO with the two surfaces was also studied with density functional theory. Both surfaces adsorb CO molecularly at low temperatures but in markedly different forms. On the LaB₆(1 1 1) surface CO initially adsorbs at 90 K in a form that yields a CO stretching mode at 1502-1512 cm⁻¹. With gentle annealing to 120 K, the CO switches to a bonding environment characterized by multiple CO stretch values from 1980 to 2080 cm⁻¹, assigned to one, two, or three CO molecules terminally bonded to the B atoms of a triangular B₃ unit at the (1 1 1) surface. In contrast, on the LaB₆(1 0 0) surface only a single CO stretch is observed at 2094 cm⁻¹, which is assigned to an atop CO molecule bonded to a La atom. The maximum intensity of the CO stretch vibration on the (1 0 0) surface is higher than on the (1 1 1) surface by a factor of 5. This difference is related to the different orientations of the CO molecules on the two surfaces and to reduced screening of the CO dynamic dipole moment on the (1 0 0) surface, where the bonding occurs further from the surface plane. On LaB₆(1 0 0), XPS measurements indicate that CO dissociates on the surface at temperatures above 400 K.     

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.     

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.     

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.     

Soft X-ray appearance potential spectroscopy (SXAPS) study of TiO2(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces

A soft X-ray appearance potential spectroscopy (SXAPS) apparatus with high sensitivity was built to measure non-derivative spectra. SXAPS spectra (non-derivative) of Ti 2p and O 1s for TiO₂(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces have been measured using low incident currents (about 10 μA/cm²) and a photon counting mode. Density of empty states on Ti and O sites are deduced by self-deconvoluting the spectra. The self-deconvoluted SXAPS spectra are qualitatively similar to those measured by X-ray absorption spectroscopy (XAS). The Ti 2p_3/2 spectrum shows two strong peaks which correspond to t_2g and e_g states. For the O 1s spectrum two strong peaks near the threshold are also found which can be ascribed to O 2pπ and O 2pσ states. These results suggest that the spectra almost obey the dipole selection rule, so-called the “approximate dipole selection rule”. The SXAPS spectra of Ti 2p and O 1s for the (1 1 0) and (0 0 1) surfaces resemble qualitatively, which is consistent with the XAS results. The spectra measured on the (1 1 0)-1 × 2 surface at an incident angle of 45° off normal to the surface and on the (1 1 0) surface sputtered by Ar ions indicate that SXAPS is very sensitive to the surface electronic states.     

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.     

In-situ study of the catalytic oxidation of CO on a Pt(1 1 0) surface using ambient pressure X-ray photoelectron spectroscopy

CO and O₂ co-adsorption and the catalytic oxidation of CO on a Pt(1 1 0) surface under various pressures of CO and O₂ (up to 250 mTorr) are studied using ambient pressure X-ray photoelectron spectroscopy (APXPS) and mass spectrometry. There is no surface oxide formation on Pt under our reaction conditions. CO oxidation in this pressure (<500 mTorr), O₂ to CO ratio (<10), and temperature (150 °C) regime is consistent with the Langmuir-Hinshelwood reaction mechanism. Our findings provide in-situ surface chemical composition data of the catalytic oxidation of CO on Pt(1 1 0) at total pressures below 1 Torr.     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

Carbon monoxide adsorption on Co deposited Pt(1 0 0)-hex: IRRAS and LEED investigations

Infrared reflection absorption spectroscopy (IRRAS) was used to investigate carbon monoxide (CO) adsorption on Pt(1 0 0) surfaces deposited with Co layers with different thicknesses. Pt(1 0 0) surfaces cleaned in ultrahigh vacuum showed surface reconstruction, i.e., Pt(1 0 0)-hex: two absorption bands ascribable to adsorbed CO on the 1 × 1 surface and hex domains emerge at 2086 and 2074 cm⁻¹, respectively, after 1.0 L CO exposure. Deposition of a 0.3-nm-thick-Co layer on Pt(1 0 0)-hex at 333 K changes the low-energy electron diffraction (LEED) pattern from hex to p(1 × 1), indicating that the deposited Co lifts the reconstruction. The IRRAS spectrum for 1.0-L-CO-exposed Co_0.3 nm/Pt(1 0 0)-hex fabricated at 333 K yields a single absorption band at 2059 cm⁻¹. For Co_0.3 nm/Pt(1 0 0)-hex fabricated at 693 K, the LEED pattern shows a less-contrasted hex and the pattern remains nearly unchanged even after CO exposure of 11 L, although only 1.0 L CO exposure to Pt(1 0 0)-hex lifts the surface reconstruction. A Co_0.3 nm/Pt(1 0 0)-hex surface fabricated at 753 K exhibits an absorption band at 2077 cm⁻¹, which is considered to originate from CO adsorbed on the Pt-enriched surface alloy. Co_0.3 nm/Pt(1 0 0)-hex surfaces fabricated above 773 K show a clear hex-reconstructed LEED pattern, and the frequencies of the adsorbed CO bands are comparable to those of Pt(1 0 0)-hex, indicating that the deposited Co atoms are diffused near the surface region. The outermost surface of the 3.0-nm-thick-Co-deposited Pt(1 0 0)-hex is composed of Pt-Co alloy domains even at a deposition temperature of 873 K. Based on the LEED and IRRAS results, the outermost surface structures of Co_x/Pt(1 0 0)-hex are discussed.     

Interaction of CO with atomically well-defined PtxRuy/Ru(0 0 0 1) surface alloys

The interaction of CO with structurally well-defined Pt_xRu_y surface alloys supported on Ru(0 0 0 1) was investigated by thermal desorption spectroscopy and infrared reflection-absorption spectroscopy. The surface composition and the distribution of the surface atoms were controlled by high resolution scanning tunneling microscopy. On these surfaces, which have a nearly random distribution of the two surface species, the adsorption (and desorption) of CO is strongly modified compared to the pure elemental surfaces, by strain effects and electronic ligand effects. CO adsorbs exclusively in a linear configuration on Pt and Ru atoms for all surfaces investigated. The adsorption energy of CO is lowered on the alloy surfaces with respect to both Pt(1 1 1) and Ru(0 0 0 1), similar as for pseudomorphic monolayer Pt films. For both Pt and Ru sites the adsorption strength decreases with increasing Pt concentration.     

Sulfur poisoning of the CO adsorption on Co(0 0 0 1)

CO adsorption on a sulfur covered cobalt surface at 185 K has been studied using XPS, TDS, LEED, and WF measurements. As in the case of CO adsorption on the clean Co(0 0 0 1) surface, CO adsorbs and desorbs molecularly and no dissociation was observed. The saturation coverage of CO decreases linearly from 0.54 ML to 0.27 ML when the S pre-coverage increases to 0.25 ML. The WF increased during CO adsorption, but did not reach the value obtained for CO adsorption on the clean surface. The smaller work function change is explained by the reduced adsorption of CO on the sulfur-precovered surface. A reduction in the activation energy of desorption for CO from 113 kJ/mol to 88 kJ/mol was observed indicating weaker bonding of the CO molecules to the surface. The behavior of the CO/S/Co(0 0 0 1) system was explained by a combination of steric and electronic effects.     

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).     

Interaction of copper with sulfur on the sulfur-terminated Si(1 1 1)-(7 × 7) surface

The adsorption of S₂ on the Si(1 1 1)-(7 × 7) surface and the interaction of copper and sulfur on this sulfur-terminated Si(1 1 1) surface have been studied using synchrotron irradiation photoemission spectroscopy and scanning tunneling microscopy. The adsorption of S₂ at room temperature results in the passivation of silicon dangling bonds of Si(1 1 1)-(7 × 7) surface. Excessive sulfur forms S_n species on the surface. Copper atoms deposited at room temperature directly interact with S-adatoms through the formations of Cu-S bonds. Upon annealing the sample at 300 °C, CuS_x nanocrystals were produced on the sulfur-terminated Si(1 1 1) surface.     

Surface (electro-)chemistry on Pt(1 1 1) modified by a Pseudomorphic Pd monolayer

The formic acid and methanol oxidation reaction are studied on Pt(1 1 1) modified by a pseudomorphic Pd monolayer (denoted hereafter as the Pt(1 1 1)-Pd_1 ML system) in 0.1 M HClO₄ solution. The results are compared to the bare Pt(1 1 1) surface. The nature of adsorbed intermediates (CO_ad) and the electrocatalytic properties (the onset of CO₂ formation) were studied by FTIR spectroscopy. The results show that Pd has a unique catalytic activity for HCOOH oxidation, with Pd surface atoms being about four times more active than Pt surface atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO₂ is observed at low potentials. This indicates that the reaction can proceed on Pd at low potentials without the typical “poison” formation. In contrast to its high activity for formic acid oxidation, the Pd film is completely inactive for methanol oxidation. The FTIR spectra show that neither adsorbed CO is formed on the Pd sites nor significant amounts of CO₂ are produced during the electrooxidation of methanol.     

The surface structure of Fe3O4(1 1 1) films as studied by CO adsorption

We have studied adsorption of CO on Fe₃O₄(1 1 1) films grown on a Pt(1 1 1) substrate by temperature programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and high resolution electron energy loss spectroscopy (HREELS). Three adsorption states are observed, from which CO desorbs at ∼110, 180, and 230 K. CO adsorbed in these states exhibits stretching frequencies at ∼2115-2140, 2080 and 2207 cm⁻¹, respectively. The adsorption results are discussed in terms of different structural models previously reported. We suggest that the Fe₃O₄(1 1 1) surface is terminated by 1/2 ML of iron, with an outermost 1/4 ML consisting of octahedral Fe²⁺ cations situated above an 1/4 ML of tetrahedral Fe³⁺ ions, in agreement with previous theoretical calculations. The most strongly bound CO is assigned to adsorption to Fe³⁺ cations present on the step edges.     

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.     

Adsorption and reactivity of SO2 on Ir(1 1 1) and Rh(1 1 1)

The adsorption and reactivity of SO₂ on the Ir(1 1 1) and Rh(1 1 1) surfaces were studied by surface science techniques. X-ray photoelectron spectroscopy measurements showed that SO₂ was molecularly adsorbed on both the Ir(1 1 1) surface and the Rh(1 1 1) surface at 200 K. Adsorbed SO₂ on the Ir(1 1 1) surface disproportionated to atomic sulfur and SO₃ at 300 K, whereas adsorbed SO₂ on the Rh(1 1 1) surface dissociated to atomic sulfur and oxygen above 250 K. Only atomic sulfur was present on both surfaces above 500 K, but the formation process and structure of the adsorbed atomic sulfur on Ir(1 1 1) were different from those on Rh(1 1 1). On Ir(1 1 1), atomic sulfur reacted with surface oxygen and was completely removed from the surface, whereas on Rh(1 1 1), sulfur did not react with oxygen.     

Initial stages of iron silicide formation on the Si(1 0 0)2 × 1 surface

The initial stages of iron silicide growth on the Si(1 0 0)2 × 1 surface during solid-phase synthesis were investigated by photoelectron spectroscopy using synchrotron radiation. The experiments were made on iron films of 1-50 monolayer (ML) thickness in the temperature range from room temperature to 750 °С. Our results support the existence of three stages in the Fe deposition on Si(1 0 0) at room temperature, which include formation of the Fe-Si solid solution, Fe₃Si silicide and an iron film. The critical Fe dose necessary for the solid solution to be transformed to the silicide is found to be 5 ML. The solid-phase reaction was found to depend on the deposited metal dose. At 5 ML, the reaction begins at 60 °С, and the solid-phase synthesis leads to the formation of only metastable silicides (FeSi with the CsCl-type structure, γ-FeSi₂ and α-FeSi₂). A specific feature of this process is Si segregation on the silicide films. At a thickness of 15 ML and more, we observed only stable phases, namely, Fe₃Si, ε-FeSi and β-FeSi₂.     

Surface chemistry of NO and NO2 on the Pt(1 1 0)-(1 × 2) surface: A comparative study

The surface chemistry of NO and NO₂ on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N₂ and N₂O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO₂ decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO₂/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.     

Formation and characterization of Au/Pd surface alloys on Pd(1 1 1)

The formation of alloys by adsorbing gold on a Pd(1 1 1) single crystal substrate and subsequently annealing to various temperatures is studied in an ultrahigh vacuum by means of Auger and X-ray photoelectron spectroscopy. The nature of the alloy surface is probed by CO chemisorption using temperature-programmed desorption and reflection-absorption infrared spectroscopy. It is found that gold grows in a layer-by-layer fashion on Pd(1 1 1) at 300 K, and starts to diffuse into the bulk after annealing to above ∼600 K. Alloy formation results in a ∼0.5 eV binding energy decrease of the Au 4f XPS signals and a binding energy increase of the Pd 3d features of ∼0.8 eV, consistent with results obtained for the bulk alloy. The experimentally measured CO desorption activation energies and vibrational frequencies do not correlate well with the surface sites expected from the bulk alloy composition but are more consistent with significant preferential segregation of gold to the alloy surface.