One-dimensional confinement in heterogeneous catalysis: Trapped oxygen on RuO2(110) model catalysts

With temperature programmed reaction (TPR) experiments and kinetic Monte Carlo (kMC) simulations of coadsorbed oxygen and HCl on the RuO₂(110) surface we studied the thermal stabilization of dissociatively adsorbed oxygen. Due to one-dimensional confinement single surface O atoms can be trapped by surface chlorine atoms so that surface oxygen is not able to desorb from the RuO₂(110) surface at the expected temperature of 420 K. Trapped oxygen needs desorption temperatures as high as 700 K where it recombines with bridging O from RuO₂(110) to form O₂. Kinetic modeling of catalytic reactions with dimensional confinement of their reaction intermediates on the catalyst's surface requires the application of kinetic Monte Carlo simulations which are beyond the mean field approach.     

Direct comparison of the reactivity of the non-oxidic phase of Ru(0 0 0 1) and the RuO2 phase in the CO oxidation reaction

Applying in situ surface X-ray diffraction (SXRD) together with on-line mass spectrometry during the CO oxidation over Ru(0 0 0 1) allows a direct comparison of the reactivity of the non-oxidic state with that of the RuO₂(1 1 0) covered surface. This comparison reveals that the RuO₂(1 1 0) surface is a catalytically active phase at least as active as the non-oxidic phase. At high CO and O₂ pressures of 200 mbar and temperatures above 550 K, the CO oxidation reaction does not proceed isothermally on the RuO₂(1 1 0) surface. The released reaction heat leads rather to an increase of the sample temperature of up to 130 K accompanied by a self-acceleration of the CO oxidation reaction.     

Oxidation and reduction of thin Ru films by gas plasma

The oxidation and reduction of Ru thin films grown on a Si(1 0 0) surface were studied by X-ray photoemission spectroscopy (XPS). Ru thin films were oxidized with O₂ plasma generated by an rf discharge, and their XPS spectra were measured. The spectra were decomposed into several components for Ru suboxides attributable to different stages of oxidation. After sufficient exposure to oxygen, a stoichiometric rutile RuO₂ layer was found to have formed near the surface. Thermal annealing at 500 K resulted in a thicker RuO₂ layer. Experiments demonstrated that the Ru oxide layer can be removed by H(D) atoms via the desorption of water molecules.     

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.     

Stability of gold nanostructures on rutile TiO2(110) surface

The adsorption of gold atoms and formation of nanostructures on the rutile TiO₂(110) surface with different degree of oxygen reduction was studied from first principles. The Au atoms adsorb strongest at oxygen vacancy sites. Starting from a very low coverage limit the potential energy profiles or diffusion paths of the adsorbed Au monomers and dimers were calculated. Stable structures of two to nine Au atoms arranged in finite and infinite rows and in the shape of finite-size clusters were determined. All these structures are found to bind to the reduced surface stronger than 2 eV/atom. The elongated Au row-like structures bind by about 0.1 eV stronger than 3D clusters, suggesting a preference for the 1D-like Au growth mode on the missing-row reconstructed TiO₂(110).     

A first principles study of the adsorption and dissociation of CO<Subscript>2</Subscript> on the δ-Pu (111) surface

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO₂ and the corresponding partially dissociated (CO + O) and completely dissociated (C + O + O) products on the δ-Pu (111) surface. The completely dissociated C + O + O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO + O (5.08 eV), with molecular CO₂ adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO₂ molecule physisorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO₂ molecule with bond angles of 117°–130° and the elongation of the CO bond. For CO + O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100°–172° with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO₂ and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study.     

Electronic band structures of low-dimensional adsorbate systems: Rare-gas adsorption on transition metals

Angle-resolved photoemission data are dis-cussed for five different Xe adlayers which exhibit electronic structures of different dimensionalities. Xe adsorption on Ni (110)-(1 × 2)-3Hand the (×) R30^° Xe layer on Ru (001) reveal two-dimensional (2D) Xe-derived band structures that are characteristic for hexagonal rare-gas layers. Different Xe 5p dispersion widths on Ni and on Ru are found due to the difference in the Xe-Xe nearest-neighbor distance. For three rare-gas systems (two different Xe coverages on hydrogen-modified Pt (110)-(1 × 2)-H and Kr step decoration on a Pt (997) surface) true one-dimensional (1D) band structures are found. For Xe step adsorption on Pt (997), electronic localized (0D) behavior is observed due to an enlarged Xe-Xe separation. The qualitative differences of the band structures in the case of 2D, 1D and 0D rare-gas systems are demonstrated and are explained by the different dimensionalities of the various structures. Received: 3 August 2000 / Accepted: 4 August 2000 / Published online: 7 March 2001     

Reactivity at the oxygen/titania interface and the related charge transfer

The present paper reports the reactivity between TiO₂ and oxygen and the related charge transfer at 298 and 1,073 K. The studies were performed using work function measurements. It was found that oxidation of TiO₂ at 1,073 K and p(O₂) = 75 kPa, initially standardized at 1,173 K and p(O₂) = 10 Pa, results in work function changes that are consistent with the theoretical model of the charge transfer during oxygen chemisorption and oxygen incorporation at the absence of structural transitions. However, oxidation of TiO₂ at 298 K, p(O₂) = 75 kPa, which has been initially standardized at 1,173 K in extremely reducing conditions at p(O₂) = ∼10⁻¹⁰ Pa, results in work function changes that are consistent with low-dimensional structural changes of the surface layer. It is shown that oxidation of strongly reduced TiO₂ at 298 K results in a decrease of work function, which cannot be explained without assuming the structural changes of the outermost surface layer.     

Enhanced gas-sensing behaviour of Ru-doped SnO2 surface: A periodic density functional approach

A theoretical study on Ru-doped rutile SnO₂(1 1 0) surface has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA-RPBE) level with a periodic supercell approach. Electronic structure analysis was performed based on the band structure and partial density of states. The results provide evidence that the electronic structures of SnO₂(1 1 0) surface are modified by the surface Ru dopant, in which Ru 4d orbital are located at the edge of the band gap region. It is demonstrated that molecular oxygen adsorption characteristics on stoichiometric SnO₂(1 1 0) surface are changed from endothermic to exothermic due to the existence of surface Ru dopant. The dissociative adsorption of molecular oxygen on the Ru_5c/SnO₂(1 1 0) surface is exothermic, which indicates that Ru could act as an active site to increase the oxygen atom species on SnO₂(1 1 0) surface. Our present study reveals that the Ru dopant on surface is playing both electronic and chemical role in promoting the SnO₂ gas-sensing property.     

Molecular origins of surface poisoning during CO oxidation over RuO2(1 1 0)

Metal oxides are of interest as environmental oxidation catalysts, but practical applications are often limited by poorly understood surface poisoning processes. RuO₂ is active for CO oxidation under UHV conditions but is deactivated by some surface poisoning processes at ambient pressures. In this work, we report kinetic models of surface poisoning during CO oxidation over RuO₂(1 1 0), based on data obtained from plane-wave, supercell DFT calculations. While a surface carbonate is stable at low O₂ pressures and high CO₂ exposures, it is not stable under catalytic conditions. A surface bicarbonate is more stable and deactivates the RuO₂ surface over a wide range of CO and oxygen pressures in the presence of trace amounts of water.     

Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

Infrared (IR) spectroscopy of chemisorbed C₆₀ on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm^-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C₆₀/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules. Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C₆₀ molecules, which results in rather small values (∼2×10⁹ s^-1 for Ag and Au, and ∼1.6×10⁹ s^-1for Cu), consistent with a marked metallic character of the adsorbed molecules. Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C₆₀ deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron–phonon coupling with induced surface states. Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002     

Al2O3 supported Ru catalysts prepared by thermolysis of Ru3(CO)12 for catalytic wet air oxidation

Low loading catalysts Ru/γ-Al₂O₃ and Ru-Ce/γ-Al₂O₃ were prepared by thermolysis of Ru₃(CO)₁₂ on γ-Al₂O_3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru_A and Ru_B) were detected during the Ru₃(CO)₁₂ decomposition process due to chemical interaction with the active OH groups on the surface of Al₂O₃ support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H₂, and RuO₂ was formed with minor amounts of Ru⁰. When the temperature was increased to 773 K to heat the sample, the ratio of Ru⁰ to RuO₂ increased. However, after the addition of CeO₂, only RuO₂ was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO₂ further enhanced number of effectively active sites on the cluster-derived catalyst surface.     

Intimate interplay of theory and experiments in model catalysis

We briefly summarize our joint effort to understand catalytic reactions on the model catalyst RuO₂(1 1 0) on the atomic scale, applying state-of-the-art density functional theory calculations and surface chemical characterizations in parallel. This intimate theory/experiment interplay allows us to gain new and deep insights into a catalytic system under investigation and to save recourses such as experimental and computing time as well as (wo)man power. Here we illustrate the utility of this intimate theory/experiment approach with a variety of recent examples related to the extraordinary activity of RuO₂. The identification of RuO₂(1 1 0) as the catalytically active state in the oxidation of CO on Ru(0 0 0 1) (Science 287 (2000) 1474) triggered a paradigm shift in model catalysis from the view of a rigid catalyst towards a structural and chemically flexible catalyst which adapts itself to the reaction conditions.     

XPS investigations of ruthenium deposited onto representative inner surfaces of nuclear reactor containment buildings

In the case of a hypothetical severe accident in a nuclear power plant, interactions of gaseous RuO₄ with reactor containment building surfaces (stainless steel and epoxy paint) could possibly lead to a black Ru-containing deposit on these surfaces. Some scenarios include the possibility of formation of highly radiotoxic RuO₄(g) by the interactions of these deposits with the oxidizing medium induced by air radiolysis, in the reactor containment building, and consequently dispersion of this species. Therefore, the accurate determination of the chemical nature of ruthenium in the deposits is of the high importance for safety studies. An experiment was designed to model the interactions of RuO₄(g) with samples of stainless steel and of steel covered with epoxy paint. Then, these deposits have been carefully characterised by scanning electron microscopy (SEM/EDS), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The analysis by XPS of Ru deposits formed by interaction of RuO₄(g), revealed that the ruthenium is likely to be in the IV oxidation state, as the shapes of the Ru 3d core levels are very similar with those observed on the RuO₂·xH₂O reference powder sample. The analysis of O 1s peaks indicates a large component attributed to the hydroxyl functional groups. From these results, it was concluded that Ru was present on the surface of the deposits as an oxyhydroxide of Ru(IV). It has also to be pointed out that the presence of “pure” RuO₂, or of a thin layer of RuO₃ or Ru₂O₅, coming from the decomposition of RuO₄ on the surface of samples of stainless steel and epoxy paint, could be ruled out. These findings will be used for further investigations of the possible revolatilisation phenomena induced by ozone.     

CO adsorption on the reduced RuO2(1 1 0) surface

The O-bridge atoms on a stoichiometric RuO₂(1 1 0) surface were removed by reaction with CO. The resulting reduced surface was then further exposed to CO. By means of thermal desorption spectroscopy and high-resolution electron energy-loss spectroscopy three adsorbed CO states were identified on bridge sites and assigned to double-bonded, single-bonded, and single-bonded species in the vicinity of O-bridge residues, respectively.     

CO和O2分子与TiO2(110)表面负载Pt单原子的相互作用

Pt单原子在低温CO氧化反应中具有很高的催化活性. 利用扫描隧道显微术与密度泛函理论,研究了Pt单原子在还原性TiO₂(110)表面的吸附行为及其与CO和O₂分子的相互作用. 研究发现在80 K低温下,TiO₂表面的氧空位缺陷是Pt单原子的最优吸附位. 将CO和O₂分子分别通入Pt单原子吸附后的TiO₂表面,研究相应的吸附构型. 实验表明在低覆盖度下,单个Pt原子会俘获一个CO分子,CO分子同时与表面次近邻的五配位Ti原子(Ti_5c)成键,进而形成非对称的Pt-CO 复合物构型. 将样品从80 K升温到100 K后,TiO₂表面的CO分子会迁移到Pt-CO处形成Pt-(CO)₂的复合结构. 对于O₂分子,单个Pt原子同样会吸附一个O₂分子,O₂分子也会与最近邻或次近邻的Ti_5c原子成键形成两种Pt-O₂构型. 这些结果在单分子尺度上揭示了CO和O₂与Pt单原子的相互作用,呈现了CO与O₂反应中的初始状态.     

The adsorption of fluor-carbon complexes on GaAs(110) studied by electron energy loss spectroscopy

The room temperature adsorption of CF₃COOH, CH₃COOH and CO on cleaved GaAs(110) surfaces has been studied by vibrational electron energy loss spectroscopy (HRELS), second derivative electron energy spectroscopy (ELS) and electron diffraction (LEED). CO does not adsorb on the GaAs surfaces in measurable quantities. Acetic acid CH₃COOH is dissociatively adsorbed as an acetate bonded to Ga surface atoms with the split-off hydrogen on As surface atoms. The fluorated acid CF₃COOH decomposes via an acetate intermediate CF₃COO into active CF₃ groups which adsorb on Ga surface atoms. The split-off hydrogen sticks to surface As atoms while the generated CO₂ desorbs. The adsorption models are consistent with the LEED c(2×2) superstructure observed after saturated adsorption of both acids.     

Oxidation of graphene on Ru(0 0 0 1) studied by scanning tunneling microscopy

The oxidation of graphene layer on Ru(0 0 0 1) has been investigated by means of scanning tunneling microscopy. Graphene overlayer can be formed by decomposing ethyne on Ru(0 0 0 1) at a temperature of about 1000 K. The lattice mismatch between the graphene overlayer and the substrate causes a moiré pattern with a superstructure in a periodicity of about 30 Å. The oxidation of graphene/Ru(0 0 0 1) was performed by exposure the sample to O₂ gas at 823 K. The results showed that, at the initial stage, the oxygen intercalation between the graphene and the Ru(0 0 0 1) substrate takes place at step edges, and extends on the lower steps. The oxygen intercalation decouples the graphene layer from the Ru(0 0 0 1) substrate. More oxygen intercalation yields wrinkled bumps on the graphene surface. The oxidation of graphene, or the removal of carbon atoms can be attributed to a process of the combination of the carbon atoms with atomic oxygen to form volatile reaction products. Finally, the Ru(0 0 0 1)-(2 × 1)O phase was observed after the graphene layer is fully removed by oxidation.     

CO adsorption on oxygen-modified molybdenum surfaces

Structures of carbon monoxide layers on the oxygen-modified Mo(1 1 0) and Mo(1 1 2) surfaces have been investigated by means of density-functional (DFT) calculations. It is found that CO molecules adsorb at hollow sites on the O/Mo(1 1 0) surface and nearly atop Mo atoms on the O/Mo(1 1 2) surface. The favorable positions for adsorption are shown to be near protrusions of electron density above the Mo surface atoms. The presence of oxygen on the molybdenum surface significantly reduces the binding energy of the CO molecule with the substrate; on the oxygen-saturated Mo(1 1 0) surface, the adsorption of CO is completely blocked. The calculated local densities of states (LDOS) demonstrate that the O 2s peak for O adsorbed on Mo(1 1 0) surface is at −19 eV (with respect to the Fermi level), while for the oxygen atom of an adsorbed CO molecule the related 3σ molecular orbital gives rise to a peak at −23 eV. This difference stems from the bonding of the O atom either with Mo surface for adsorbed O or with C atom in adsorbed CO, and therefore the position of the O 2s peak in photoemission spectra can serve as a convincing argument in favor of either the presence or absence of the CO dissociation on Mo surfaces.     

Oxygen adsorption on the LaB6(100), (110) and (111) surfaces

Oxygen adsorption on the LaB₆(100), (110) and (111) clean surfaces has been studied by means of UPS, XPS and LEED. The results on oxygen adsorption will be discussed on the basis of the structurs and the electronic states on the LaB₆(100), (110) and (111) clean surfaces. The surface states on LaB₆(110) disappear at the oxygen exposure of 0.4 L where a c(2 × 2) LEED pattern disappears and a (1 × 1) LEED pattern appears. The work function on LaB₆(110) is increased to ～3.8 eV by an oxygen exposure of ～2 L. The surface states on LaB₆(111) disappear at an oxygen exposure of ～2 L where the work function has a maximum value of ～4.4 eV. Oxygen is adsorbed on the surface boron atoms of LaB₆(111) until an exposure of ～2 L. Above this exposure, oxygen is adsorbed on another site to lower the work function from ～4.4 to ～3.8 eV until an oxygen exposure of ～100L. The initial sticking coefficient on LaB₆(110) has the highest value of ～1 among the (100), (110) and (111) surfaces. The (100) surface is most stable to oxygen among these surfaces. It is suggested that the dangling bonds of boron atoms play an important role in oxygen adsorption on the LaB₆ surfaces.