Electronic decoupling of surface layers from bulk and its influence in oxidation catalysis: A molecular beam study

Interactions between oxygen and Pd-surfaces have important implications, especially towards oxidation reactions, and influence of subsurface oxygen to oxidation reactions is the focus of the present study. In our efforts to understand the above aspects, CO oxidation reactions have been carried out with mixed molecular beam (MB), consisting CO and O₂, on Pd(1 1 1) surfaces under a wide variety of conditions (T = 400-900 K, CO:O₂ = 7:1 to 1:10). A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd subsurface layers, and its significant influence towards CO oxidation at high temperatures (≥600 K). Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (θ_O-sub), above which the reactive CO adsorption occurs on the surface and simultaneous CO₂ production begins. There is also a significant time delay (Γ) observed between the onset of oxygen adsorption and CO adsorption (and CO₂ production). Above studies suggest an electronic decoupling of oxygen covered surface and subsurface layers, which is slightly oxidized, from the metallic bulk, which induces CO adsorption at high temperatures and simultaneous oxidation to CO₂.     

Deep reduction behavior of iron oxide and its effect on direct CO oxidation

Reduction of metal oxide oxygen carrier has been attractive for direct CO oxidation and CO₂ separation. To investigate the reduction behaviors of iron oxide prepared by supporting Fe₂O₃ on γ-Al₂O₃ and its effect on CO oxidation, fluidized-bed combustion experiments, thermogravimetric analyzer (TGA) experiments, and density functional theory (DFT) calculations were carried out. Gas yield (γCO₂) increases significantly with the increase of temperature from 693 K to 1203 K, while carbon deposition decreases with the increase of temperature from 743 K to 1203 K, where temperature is a very important factor for CO oxidation by iron oxide. Further, it were quantitatively detected that the interaction between CO and Fe₂O₃, breakage of O-Fe bonds and formation of new C-O bonds, and effect of reduction degree were quantitatively detected. Based on adsorptions under different temperatures and reducing processes from Fe³⁺ into Fe²⁺, Fe⁺ and then into Fe, it was found that Fe²⁺ → Fe⁺ was the reaction-controlling step and the high oxidation state of iron is active for CO oxidation, where efficient partial reduction of Fe₂O₃ into FeO rather than complete reduction into iron may be more energy-saving for CO oxidation.     

Thermal decomposition of Mo(CO)6 on thin Al2O3 film: A combinatorial investigation by XPS and UPS

A thin and homogeneous alumina film was prepared by deposition and oxidation of aluminum on a refractory Re(0 0 0 1) substrate under ultrahigh vacuum conditions. X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and high-resolution electron-energy-loss spectroscopy (HREELS) demonstrate that the oxide film is long-range ordered, essentially stoichiometric and free from surface hydroxyl groups. The chemisorption and thermal decomposition of Mo(CO)₆ on the Al₂O₃ film were investigated by means of XPS and UPS. Mo(CO)₆ adsorbs molecularly on the oxide film at 100 K; however, thermal decomposition of the adsorbate occurs upon annealing at high temperatures. Consequently the metallic molybdenum clusters are deposited on the thin alumina film via complete decarbonylation of Mo(CO)₆.     

Highly active surfaces for CO oxidation on Rh, Pd, and Pt

Studies show that the rate of CO oxidation on Pt-group metals at temperatures between 450 and 600 K and pressures between 1 and 300 Torr increases markedly with an increase in the O₂/CO ratio above 0.5. The catalytic surfaces, formed at discrete O₂/CO ratios >0.5, exhibit rates 2-3 orders of magnitude greater than those rates observed for stoichiometric reaction conditions and similar reactant pressures or previously in ultrahigh vacuum studies at any reactant conditions and extrapolate to the collision limit of CO in the absence of mass transfer limitations. The O₂/CO ratios required to achieve these so-called “hyperactive” states (where the reaction probabilities of CO are thought to approach unity) for Rh, Pd, and Pt relate directly to the adsorption energies of oxygen, the heats of formation of the bulk oxides, and the metal particle sizes. Auger spectroscopy and X-ray photoemission spectroscopy reveal that the hyperactive surfaces consist of approximate 1 ML of surface oxygen. In situ polarization modulation reflectance absorption infrared spectroscopy measurements coupled with no detectable adsorbed CO. In contrast, under stoichiometric O₂/CO conditions and similar temperatures and pressures, Rh, Pd, and Pt are essentially saturated with chemisorbed CO and exhibit far less activity for CO oxidation.     

Surface oxidation of NiCo alloy: A comparative X-ray photoelectron spectroscopy study in a wide pressure range

Oxidation of NiCo alloy has been studied under two pressure regimes, 5 × 10⁻¹⁰ and 5 × 10⁻¹ bar, by X-ray photoelectron spectroscopy (XPS). The aim of this work is to investigate the synergetic effect between the two alloy components during the initial stages of oxidation. The results showed that at low oxygen pressure, segregation and preferential oxidation of cobalt takes place, while oxidation of nickel is largely suppressed. The species dominating the surface is CoO but small amount of metallic cobalt still remains even after prolonged oxidation at 670 K. At 0.5 bar O₂ pressure, alloy oxidation was found to be temperature depended. From 420 K to 520 K, cobalt is completely transformed to CoO and the Ni:Co atomic ratio at the surface approaches a minimum, similar to the observations at low pressure regime. However, at higher temperatures (from 520 K to 720 K), nickel is re-segregated on the surface, in the expense of cobalt, while CoO is further oxidized to Co₃O₄. At this temperature range formation of mixed Ni-Co-O spinel-like oxides is probable as supported by the characteristic modifications of the Ni 2p_3/2 photoelectron peak and the increase of the Ni:Co atomic ratio.     

Preferential surface oxidation of Gd in Gd5Ge4

Gd oxidizes preferentially at the (0 1 0) surface of Gd₅Ge₄. This is consistent with thermodynamic data for the bulk oxides. Upon oxidation in vacuum, the gadolinium oxide displaces or covers the Ge. Oxidation is more extensive at 600 K than at 300 K, because more oxygen is incorporated into the surface and the shift of the Gd binding energy is larger.     

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.     

Interfacial electronic structure and ion beam induced effect of anatase TiO2 surface modified by Pd nanoparticles

Anatase TiO₂ surface could be modified by Pd nanoparticles using an electrochemical deposition method. Surface morphology, light absorption and interfacial electronic structures were studied by field emission scanning electron microscopy (FE-SEM), UV-visible reflectance absorption, X-ray diffraction (XRD) crystallography, and depth-profiling X-ray photoelectron spectroscopy (XPS). On the basis of XRD patterns, Pd 3d XPS and valance band spectra, the as-deposited overlayer Pd is metallic, with no detectable Pd oxides. The optical band gap of TiO₂ decreases from 3.25 to 3.14 eV upon Pd deposition. The XPS spectra with Ar⁺ ion sputtering show that 4+ oxidation state of Ti dramatically changes to lower (3+ and 2+) oxidation states. As a result of this, oxygen defects are created in the bulk while the oxygen diffuses outward to likely form hydroxyl group on the surface. The Pd 3d XPS peak shifts by +0.6 eV to a higher BE position, and the density of state at the Fermi level is more or less reduced. It appears that the overlayer Pd becomes less metallic, plausibly due to TiO₂ support and/or size effect. No critical interfacial interaction between Pd and TiO₂ was observed by XPS.     

In situ XPS study of Pd(1 1 1) oxidation at elevated pressure, Part 2: Palladium oxidation in the 10 mbar range

The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 0.4 mbar O₂. The in situ XPS data were complemented by ex situ TPD results. A number of oxygen species and oxidation states of palladium were observed in situ and ex situ. At 430 K, the Pd(1 1 1) surface was covered by a 2D oxide and by a supersaturated O_ads layer. The supersaturated O_ads layer transforms into the Pd₅O₄ phase upon heating and disappears completely at approximately 470 K. Simultaneously, small clusters of PdO, PdO seeds, are formed. Above 655 K, the bulk PdO phase appears and this phase decomposes completely at 815 K. Decomposition of the bulk oxide is followed by oxygen dissolution in the near-surface region and in the bulk. The oxygen species dissolved in the bulk is more favoured at high temperatures because oxygen cannot accumulate in the near-surface region and diffusion shifts the equilibrium towards the bulk species. The saturation of the bulk “reservoir” with oxygen leads to increasing the uptake of the near-surface region species. Surprisingly, the bulk PdO phase does not form during cooling in 0.4 mbar O₂, but the Pd₅O₄ phase appears below 745 K. This is proposed to be due to a kinetic limitation of PdO formation because at high temperature the rate of PdO seed formation is compatible with the rate of decomposition.     

Morphology and composition of nanoscale surface oxides on Fe–20Cr–18Ni{1 1 1} austenitic stainless steel

Surface oxidation ranging from initial stages to the onset of passive oxide layer formation have been investigated on Fe–20Cr–18Ni{1 1 1} single crystal surface by X-ray photoelectron spectroscopy (XPS). Surface segregation of the alloying elements and the morphology of the surface oxide nanostructure were characterized quantitatively by inelastic electron background analysis. Our results demonstrate that by increasing the oxidation temperature the relative concentrations of Fe²⁺ and Fe³⁺ cations increase due to their enhanced mobility. Higher temperature also improves the mobility of chromium, thus enhancing its segregation to the oxygen-rich surface and thereby reinforcing the passive layer on the alloy. This is in agreement with the results showing the sudden decrease in oxide film thickness at the oxidation temperatures exceeding 600 K. Additionally, a pronounced segregation of metallic nickel is found in the interface between the surface oxide layer and the bulk alloy.     

The iron oxidation state in Mg-Al-Fe mixed oxides derived from layered double hydroxides: An XPS study

Mixed oxides with large surface area and high thermal stability can be obtained by thermal treatment of the layered double hydroxides (LDH). Mg-Al-Fe mixed oxide samples with varying Mg/Al ratio and 5 mol.% of Fe were prepared in this way and the iron oxidation state (Fe_ox) in these compounds was studied by X-ray photoelectron spectroscopy (XPS), using a calibration based on the relation of Fe_ox to the splitting between the O 1s and Fe 2p_3/2 centroids. The XPS results confirm Fe³⁺ as a dominant oxidation state in the studied mixed oxides. A vacuum-induced reduction of iron in the Fe₂O₃ and Mg-Al-Fe oxide samples has been observed and an influence of the Mg:Al ratio on this effect in mixed oxides has been detected. The role of the local variations of the electron density distribution in the close neighbourhood of the surface oxygen atoms in the mixed oxides in the reduction processes is discussed.     

In situ XPS study of Pd(1 1 1) oxidation. Part 1: 2D oxide formation in 10 mbar O2

The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 3 × 10⁻³ mbar O₂. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd₅O₄), the supersaturated O_ads layer, dissolved oxygen and the R 12.2° surface structure.Exposure of the Pd(1 1 1) single crystal to 3 × 10⁻³ mbar O₂ at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated O_ads layer. The supersaturated O_ads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd₅O₄, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d_5/2 components at 335.5 eV and 336.24 eV. During heating in 3 × 10⁻³ mbar O₂ the supersaturated O_ads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The “bulk” nature of the dissolved oxygen species was verified by depth profiling.During cooling in 3 × 10⁻³ mbar O₂, the oxidised Pd²⁺ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the R 12.2° structure.     

CO oxidation over Ru(0 0 0 1) at near-atmospheric pressures: From chemisorbed oxygen to RuO2

RuO₂(1 1 0) was formed on Ru(0 0 0 1) under oxygen-rich reaction conditions at 550 K and high pressures. This phase was also synthesized using pure O₂ and high reaction temperatures. Subsequently the RuO₂ was subjected to CO oxidation reaction at stoichiometric and net reducing conditions at near-atmospheric pressures. Both in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and post-reaction Auger electron spectroscopy (AES) measurements indicate that RuO₂ gradually converts to a surface oxide and then to a chemisorbed oxygen phase. Reaction kinetics shows that the chemisorbed oxygen phase has the highest reactivity due to a smaller CO binding energy to this surface. These results also show that a chemisorbed oxygen phase is the thermodynamically stable phase under stoichiometric and reducing reaction conditions. Under net oxidizing conditions, RuO₂ displays high reactivity at relatively low temperatures (?450 K). We propose that this high reactivity involves a very reactive surface oxygen species, possibly a weakly bound, atomic oxygen or an active molecular O₂ species. RuO₂ deactivates gradually under oxidizing reaction conditions. Post-reaction AES measurements reveal that this deactivation is caused by a surface carbonaceous species, most likely carbonate, that dissociates above 500 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.     

Interaction of O2 with Pd single crystals in the range 1-150 Torr: Oxygen dissolution and reaction

The interaction of O₂ with Pd(1 1 1), Pd(1 1 0) and Pd(1 0 0) was studied in the pressure range 1-150 Torr by the techniques of temperature programmed decomposition (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The oxidation of Pd was rate-determined by oxygen diffusion into Pd metal followed by the diffusion into PdO once the bulk oxide layer was formed. The dissolution of oxygen atoms into Pd metal followed the Mott-Cabrera model with diffusion coefficient 10⁻¹⁶ cm² s⁻¹ at 600 K and activation energy of 60-85 kJ mol⁻¹. The bulk oxide phase was formed when a critical oxygen concentration was reached in the near-surface region. The formation of PdO was characterized by a decrease in the oxygen uptake rate, the complete fading of the metallic Pd LEED pattern and an atomic ratio O/Pd of 0.15-0.7 as measured by AES. The diffusion of oxygen through the bulk oxide layer again conformed to the Mott-Cabrera parabolic diffusion law with diffusion coefficient 10⁻¹⁸ cm² s⁻¹ at 600 K and activation energy of 111-116 kJ mol⁻¹. The values for the diffusion coefficient and apparent activation energy increased as the surface atom density of the single crystals increased.     

Metal-support interactions in systems palladium deposited on oxidized tungsten surfaces

The morphology of the palladium (Pd) overlayers on oxidized tungsten (W) tips has been studied by Field Emission Microscopy (FEM). The effect of thermal treatment on the interaction of Pd with the support and chemisorption of CO on variously treated Pd-containing samples has been investigated. The results are discussed in relation to complementary macroscopic experiments by synchrotron radiation excited photoelectron spectroscopy (SRPES) and thermally programmed desorption (TPD) of carbon monoxide (CO) on a polycrystalline W foil. A distinct influence of support pre-oxidation on the Pd layer growth has been demonstrated. Two types of oxidized supports have been used: tungsten with oxygen pre-adsorbed at room temperature (RT) and then heated to 700 K (WO_x/W (RT) system) and tungsten oxidized at 1300 K (WO_x/W (1300 K) system) in situ. The surface of WO_x/W (1300 K) sample is fully oxidized in contrast to WO_x/W (RT), where the presence of un-oxidized patches has been demonstrated by SRPES measurements. A Pd layer grows on the WO_x/W (RT) surface mostly on the densely populated planes (1 1 0) and (2 1 1) of the W tip. Heating of this system up to 700 K results in disaggregation of the original Pd layer. Pd clusters on the tungsten tip oxidized at 1300 K are localized on the atomically rough (1 1 1) plane. The observed differences in CO adsorption on the aforementioned types of investigated samples can be attributed to differences in the chemical nature of their surfaces.     

Interaction of O2 with Pd single crystals in the range 1-150 Torr: Surface morphology transformations

The interaction of O₂ with Pd single crystals including Pd(1 1 1), Pd(1 1 0) and Pd(1 0 0) in the pressure range 1-150 Torr was studied using scanning tunneling microscopy (STM). The Pd single crystal surface morphologies were determined by the oxidation conditions: O₂ pressure, exposure time and treatment temperature. Oxygen dissolution into Pd metal followed by the formation of bulk oxide was observed. The dissolution of oxygen resulted in the increase of the inter-planar spacing between the first two layers, 9-14% increase after an exposure of Pd(1 1 1) to 10-25 Torr O₂ at 600 K for 10 min, and 10-20% increase after exposing Pd(1 1 0) and Pd(1 0 0) to 1 Torr O₂ at 600 K for 10 min. Elongated or semi-spherical oxide agglomerates along the steps nucleated and grew on both Pd(1 1 0) and Pd(1 0 0) surfaces after oxidation in 5-25 Torr O₂ at 600 K. When bulk PdO was formed, the single crystal surface was covered with semi-spherical agglomerates 2-4 nm in size, which tended to aggregate to form a “cauliflower-like” structure. The single crystal surface area also increased during oxidation.     

The plasma oxidation of Pd(1 0 0)

The oxidation of Pd(1 0 0) by an oxygen plasma was characterized using X-ray photoelectron spectroscopy (XPS), low energy ion scattering spectroscopy (ISS), temperature programmed desorption (TPD), and low energy electron diffraction (LEED). The oxygen uptake followed a typical parabolic profile with oxygen coverages reaching 32 ML after 1 h in the plasma; a factor of 40 higher than could be achieved by dosing molecular oxidants in ultra high vacuum. Even after adsorbing 32 ML of oxygen, XPS revealed both metallic Pd and PdO in the surface region. The R27^o LEED pattern previously attributed to a surface oxide monolayer, slowly attenuated with oxygen coverage indicating that the PdO formed poorly ordered three dimensional clusters that slowly covered the ordered surface oxide. While XPS revealed the formation of bulk PdO, only small changes in the ISS spectra were observed once the surface oxide layer was completed. The leading edges of the O₂ TPD curves showed only small shifts with increasing oxygen coverage that could be explained in terms of the lower thermodynamic stability of small oxide clusters. The desorption curves, however, could not be adequately described as simple zero order decomposition of PdO. There has been an ongoing debate in the literature about the relative catalytic activities of PdO and oxygen phases on Pd, the results indicate that any differences in the reactivity between bulk PdO and surface oxides are not associated with differences in the density of exposed Pd atoms or the decomposition kinetics of these two phases.     

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.     

Oxygen-induced nano-faceting of Ir(2 1 0)

The adsorption of oxygen and the nanometer-scale faceting induced by oxygen have been studied on Ir(2 1 0). Oxygen is found to chemisorb dissociatively on Ir(2 1 0) at room temperature. The molecular desorption process is complex, as revealed by a detailed kinetic analysis of desorption spectra. Pyramid-shaped facets with {3 1 1} and (1 1 0) orientations are formed on the oxygen-covered Ir(2 1 0) surface when annealed to T?600 K. The surface remains faceted for substrate temperatures T<850 K. For T>850 K, the substrate structure reverts to the oxygen-covered (2 1 0) planar state and does so reversibly, provided that oxygen is not lost due to desorption or via chemical reactions upon which the planar (2 1 0) structure remains. A clean faceted surface was prepared through the use of low temperature surface cleaning methods: using CO oxidation, or reaction of H₂ to form H₂O, oxygen can be removed from the surface while preserving (“freezing”) the faceted structure. The resulting clean faceted surface remains stable for T<600 K. For temperatures above this value, the surface irreversibly relaxes to the planar state.