Monte Carlo simulation of properties of monolayers and metal islands adsorbed on metallic (111) surfaces

To obtain the surface stress changes due to the adsorption of metal monolayers onto metallic surfaces, a new model derived from thermodynamic considerations is presented. Such a model is based on continuum Monte Carlo simulations with embedded atom method potentials in the canonical ensemble, and it is extended to consider the behavior on different islands adsorbed onto (111) substrate surfaces. Homoepitaxial and heteroepitaxial systems are studied. Pseudomorphic growth is not observed for small metal islands with considerable positive misfit with the substrate. Instead, the islands become compressed upon increase of their size. A simple model is proposed to interpolate between the misfits of atoms in small islands and the pseudomorphic behavior of the monolayer.

CO oxidation and NO reduction on metal surfaces: density functional theory investigations

This article reviews the accumulated theoretical results, in particular density functional theory calculations, on two catalytic processes, CO oxidation and NO reduction on metal surfaces. Owing to their importance in automotive emission control, these two reactions have generated a lot of interest in the last 20 years. Here the pathways and energetics of the involved elementary reactions under different catalytic conditions are described in detail and the understanding of the reactions is generalized. It is concluded that density functional theory calculations can be applied to catalysis to elucidate mechanisms of complex surface reactions and to understand the electronic structure of chemical processes in general. The achieved molecular knowledge of chemical reactions is certainly beneficial to new catalyst design.

Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N-2+3H(2)-->2NH(3)). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H-->NH, NH+H-->NH2 and NH2+H-->NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H-->CH and O+H-->OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors. (C) 2003 American Institute of Physics.

General trends in the barriers of catalytic reactions on transition metal surfaces

A catalyst preparation by design is one of the ultimate goals in chemistry. The first step towards this goal is to understand the origin of reaction barriers. In this study, we have investigated several catalytic reactions on some transition metal surfaces, using density functional theory. All the reaction barriers have been determined. By detailed analyses we obtain some insight into the reaction barrier. Each barrier is related to (i) the potential energy surface of reactants on the surface, (ii) the total chemisorption energy of reactants, and (iii) the metal d orbital occupancy and the reactant valency. (C) 2001 American Institute of Physics.

General trends in CO dissociation on transition metal surfaces

Dissociative adsorption is one of the most important reactions in catalysis. In this communication we propose a model aiming to generalize the important factors that affect dissociation reactions. Specifically, for a dissociation reaction, say AB -->A + B, the model connects the dissociation barrier with the association barrier, the chemisorption energies of A and B at the final state and the bonding energy of AB in the gas phase. To apply this model, we have calculated CO dissociation on Ru(0001), Rh(111), Pd(111) (4d transition metals), Os(0001), Ir(111), and Pt(111) (5d transition metals) using density function theory (DFT). All the barriers are determined. We find that the DFT results can be rationalized within the model. The model can also be used to explain many experimental observations. (C) 2001 American Institute of Physics.

A density functional theory study of the reaction of C+O, C+N, and C+H on close packed metal surfaces

Density functional theory (DFT) has been used to determine reaction pathways for several reactions taking place on Pt(111) and Cu(111) surfaces. On Pt(111), the reactions of C+O and C+N were studied, and on Cu(111) we investigated the reaction of C+H. The structures of the transition states accessed in each reaction are similar. An equivalent distance separates the reactants with the first located at a three-fold hollow site and the second close to a bridge site. Previous DFT studies have, in fact, often identified transition states of this type and in every case it is the reactant with the weaker chemisorption energy that is located close to the bridge site. An explanation as to why this is so is provided. (C) 2001 American Institute of Physics.

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

Sheets of Large Superhydrophobic Metal Particles Self Assembled on Water by the Cheerios Effect

A copper-rich cereal: Superhydrophobic copper particles show a very large Cheerios effect and rapidly self-assemble into robust sheets on the surface of water. These sheets can support objects (including water drops, see photo) placed on them, even though the irregular geometry of the particles means that they contain macroscopic holes.