Chemisorption and dissociation of carbon monoxide on rhodium surfaces

The adsorption, desorption and decomposition of CO on Rh surfaces have been investigated using field emission microscopy and thermal desorption spectroscopy. Thermal dissociation of CO cannot be detected on clean Rh surfaces at pressures up to 10^?1 Torr and temperatures below 1000 K. This holds also for atomically rough surfaces like (210). CO dissociation can be promoted under the influence of an electron beam directed to the surface, a high electric field in the presence of CO in the gas phase and by means of discharge techniques. The growth of crystallites formed by CO dissociation and the diffusion of carbon into the bulk has been followed as a function of temperature and surface structure. The tip regions around (110) are very active in these processes. Carbon crystallites on these surfaces disappear around 1000 K by diffusion into the lattice whereas crystallites present around (311) surfaces persist up to 1150 K. The results are discussed in relation to the activity of Rh in CO/H₂ reactions.     

Adsorption-desorption kinetics of carbon monoxide on rhodium polycrystalline surfaces

Adsorption isotherms, the absolute adsorption rate, and the absolute desorption rate of carbon monoxide on rhodium polycrystalline surfaces were measured in the same manner as in our previous work on palladium. The absolute adsorption rate was proportional to pressure, independent of temperature and was a slightly non-linear function of the coverage of CO. The absolute desorption rate was proportional to the coverage and was an increasing function of temperature and pressure. These results are similar to those of palladium.     

Pattern formation on carbon nanotube surfaces

Calculations of fluorine binding and migration on carbon nanotube surfaces show that fluorine forms varying surface superlattices at increasing temperatures. The ordering transition is controlled by the surface migration barrier for fluorine atoms to pass through next neighbor sites on the nanotube, explaining the transition from semi-ionic low coverage to covalent high coverage fluorination observed experimentally for gas phase fluorination between 200 and 250 degrees C. The effect of solvents on fluorine binding and surface diffusion is explored.     

Hillock formation on ion-irradiated graphite surfaces

Abstract

Scanning probe microscopy experiments show that ion irradiation of (0001) graphite results in the formation of isolated defects comprising of a few tens of atoms. We use molecular dynamics simulations and density-functional theory calculations to study the formation probabilities of these defects. We identify different defect structures which correspond to experimentally observed hillocks on graphite surfaces. We find that the predominant source of defects are vacancies and interlayer interstitials, and identify a three-atom carbon ring defect on the graphite surface.     

Pattern formation on anisotropic and heterogeneous catalytic surfaces

We review experimental and theoretical work addressing pattern formation on anisotropic and heterogeneous catalytic surfaces. These systems are typically modeled by reaction-diffusion equations reflecting the kinetics and transport of the involved chemical species. Here, we demonstrate the influence of anisotropy and heterogeneity in a simplified model, the FitzHugh-Nagumo equations. Anisotropy causes stratification of labyrinthine patterns and spiral defect chaos in bistable media. For heterogeneous media, we study the situation where the heterogeneity appears on a length scale shorter than the typical pattern length scale. Homogenization, i.e., computation of effective medium properties, is applied to an example and illustrated with simulations in one (fronts) and two dimensions (spirals). We conclude with a discussion of open questions and promising directions that comprise the coupling of the microscopic structure of the surface to the macroscopic concentration patterns and the fabrication of nanostructures with heterogeneous surfaces as templates. (c) 2002 American Institute of Physics.     

Oxide states spectroscopy of real Ge surfaces

The electronic structure of surface oxide has been investigated by measurements of internal photoemission and photoconductivity measurements for p-type single crystalline Ge specimens with real surfaces. The photo-response curves show bulk and surface effects which are separated by differential methods. Emission from the bulk into oxide states or from oxide states into the bulk result in positive or negative changes of surface conductivity. The oxide states are distributed in energy with maxima near the conduction-band edge and the valence-band edge of the oxide. Changes of the electronic structure are observed by X-irradiation and storage in laboratory air.     

Vacancy formation and CO adsorption on gold-doped ceria surfaces

We study the effect of gold doping on oxygen vacancy formation and CO adsorption on the (1 1 0) and (1 0 0) surfaces of ceria by using density functional theory, corrected for on-site Coulomb interactions (DFT + U). The Au dopant substitutes a Ce atom in the surface layer, leading to strong structural distortions. The formation of one oxygen vacancy near a dopant atom is energetically “downhill” while the formation of a second vacancy around the same dopant requires energy. When the surface is in equilibrium with gaseous oxygen at 1 atm and room temperature there is a 0.4 probability that no oxygen atom left the neighborhood of a dopant. This means that the sites where the dopant has not lost oxygen are very active in oxidation reactions. Above 400 K almost all dopants have an oxygen vacancy next to them and an oxidation reaction in such a system takes place by creating a second vacancy. The energy required to form a second vacancy is smaller on (1 1 0) than on (1 0 0). On the (1 1 0) surface, it is much easier to form a second vacancy on the doped surface than the first vacancy on the undoped surface. The energy required to form a second oxygen vacancy on (1 0 0) is comparable to that of forming the first vacancy on the undoped surface. Thus doping makes the (1 1 0) surface a better oxidant but it has a small effect on the oxidative power of the (1 0 0) surface. On the (1 1 0) surface CO adsorption results in formation of a carbonate-like structure, similar to the undoped surface, while on the (1 0 0) surface direct formation of CO₂ is observed, in contrast to the undoped surface. The Au dopant weakens the bond of the surrounding oxygen atoms to the oxide making it a better oxidant, facilitating CO oxidation.     

Oxidation and reduction of rough and flat Au surfaces

Very recently, we have shown that the oxidation pattern of very small (<0.7 nm in particle height) and larger Au nanoparticles are dissimilar, i.e. lager particles form Au(III) species upon atomic oxygen exposures, whereas this was not found for the smaller Au nanoparticles. In the present work, we found that the oxidation pattern of a flat Au surface is analogous to those of the larger Au nanoparticles, whereas a rough surface shows a similar oxidation pattern as those of the smaller particles. This result confirms that an increase of the number of undercoordinated atoms of smaller nanoparticles should be responsible for different oxidation patterns. The oxygen species formed on flat Au surfaces can readily react with CO to CO₂, whereas the oxygen species of the rough Au surface is mostly inert to the CO-oxidation, also in agreement with the results for supported Au nanoparticles.     

Tip-induced reduction of the resonant tunneling current on semiconductor surfaces

We report scanning tunneling microscope measurements showing a substantial decrease of the current, almost to zero, on the Si(111)-(7x7) reconstruction in the near-to-contact region under low bias conditions. First principles simulations for the tip-sample interaction and transport calculations show that this effect is driven by the substantial local modification of the atomic and electronic structure of the surface. The chemical reactivity of the adatom dangling bond states that dominate the electronic density of states close to the Fermi level and their spatial localization result in a strong modification of the electronic current.     

Oxidation enthalpies for reduction of ceria surfaces

The thermodynamic properties of surface ceria were investigated through equilibrium isotherms determined by flow titration and coulometric titration measurements on high-surface-area ceria and ceria supported on La-modified alumina (LA). While the surface area of pure ceria was found to be unstable under redox conditions, the extent of reduction at 873 K and a P(O₂) of 1.6 × 10⁻²⁶ atm increased with surface area. Because ceria/LA samples were stable, equilibrium isotherms were determined between 873 and 973 K on a 30-wt% ceria sample. Oxidation enthalpies on ceria/LA were found to vary with the extent of reduction, ranging from −500 kJ/mol O₂ at low extents of reduction to near the bulk value of −760 kJ/mol O₂ at higher extents. To determine whether +3 dopants could affect the oxidation enthalpies for ceria, isotherms were measured for Sm⁺³-doped ceria (SDC) and Y⁺³-doped ceria. These dopants were found to remove the phase transition observed in pure ceria below 973 K but appeared to have minimal effect on the oxidation enthalpies. Implications of these results for catalytic applications of ceria are discussed.     

Underwater restoration and retention of gases on superhydrophobic surfaces for drag reduction

Superhydrophobic (SHPo) surfaces have shown promise for passive drag reduction because their surface structures can hold a lubricating gas film between the solid surface and the liquid in contact with it. However, the types of SHPo surfaces that would produce any meaningful amount of reduction get wet under liquid pressure or at surface defects, both of which are unavoidable in the real world. In this Letter, we solve the above problem by (1)?discovering surface structures that allow the restoration of a gas blanket from a wetted state while fully immersed underwater and (2)?devising a self-controlled gas-generation mechanism that maintains the SHPo condition under high liquid pressures (tested up to 7?atm) as well as in the presence of surface defects, thus removing a fundamental barrier against the implementation of SHPo surfaces for drag reduction.     

Oxide circle formation at silicon-polymer interface

We demonstrate that precipitation of implanted erbium ions at silicon-polymer interface initiates oxidation reaction of Si(1 0 0) surface at room temperature. Oxidation reaction starts through spontaneous formation of circular patches of SiO_x and the diameter of these circles grows uniformly with time and touch each other to cover the entire surface by keeping the thickness of these patches almost fixed at 4 nm. The nucleation and in-plane growth rates of SiO_x circles are found to be dependent on the fluence of erbium-implantation, the condition of substrate and can be controlled by controlling oxygen partial pressure of the environment. In addition to the precipitation of erbium ions at silicon-polymer interface, enhancement of concentration of erbium ions was observed at periodic depths within polymer film confirming that in ultra-thin films polymer molecules form layers parallel to substrate surface due to confinement.     

On the formation of periodic structures on solid surfaces

A model is proposed to explain the formation of periodic structures produced on solid surfaces by laser radiation. The model gives rise to a system of two linear integrodifferential equations with difference kernels for temperature correction due to the specific absorption of electromagnetic energy at a certain solid surface profile and at a surface profile formed due to heat expansion resulting from temperature correction. The solution of this system reveals, that, first, periodic structures are formed as a result of the propagation of periodic profiles generated from a certain original non-periodic profile over the body surface. Second, the amplitudes of these waves grow with time only for a laser density exceeding certain critical value, i.e. the formation of periodic structures is a threshold effect relative to the laser density.     

Partial and complete reduction of O2 by hydrogen on transition metal surfaces

The metal-catalyzed reduction of di-oxygen (O₂) by hydrogen is at the heart of direct synthesis of hydrogen peroxide (HOOH) and power generation by proton exchange membrane fuel cells. Despite its apparent simplicity, how the reaction proceeds on different metals is not yet well understood. We present a systematic study of O₂ reduction on the (111) facets of eight transition metals (Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) based on periodic density functional theory (DFT-GGA) calculations. Analysis of ten surface elementary reaction steps suggests three selectivity regimes as a function of the binding energy of atomic oxygen (BE_O), delineated by the opposite demands to catalyze O–O bond scission and O–H bond formation: The dissociative adsorption of O₂ prevails on Ni, Rh, Ir, and Cu; the complete reduction to water via associative (peroxyl, peroxide, and aquoxyl) mechanisms prevails on Pd, Pt, and Ag; and HOOH formation prevails on Au. The reducing power of hydrogen is decreased electrochemically by increasing the electrode potential. This hinders the hydrogenation of oxygen species and shifts the optimal selectivity for water to less reactive metals. Our results point to the important role of the intrinsic reactivity of metals in the selectivity of O2 reduction, provide a unified basis for understanding the metal-catalyzed reduction of O₂ to H₂O and HOOH, and offer useful insights for identifying new catalysts for desired oxygen reduction products.