Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Durability of Adhesion Between Metals and Polymers

Adequate adhesion between metals and polymers is primarily the result of chemical bonds in the boundary layer. This region, however, is subject to degradation by moisture. Three modes of deterioration are observed. The first is a largely reversible weakening effect in the polymer layer near the metal oxide surface. The structure of this layer differs from that of the bulk and is influenced by the chemical and physical properties of the surface. The second is a slow transformation of the oxide by hydration and a diffusion of oxide constituents into the polymer. This process is irreversible and is influenced by the state of the surface and chemical properties of the polymer. The third is a fast deterioration of the oxide by primary corrosion usually initiating at an unprotected edge but occasionally arising within the body of a joint.     

Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm⁻³ and varying H⁺ concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H⁺ concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO₂ and RTO. The expression of the kinetic current as a function of chlorine and H⁺ concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential.     

Interactive Simulation of Rigid Body Dynamics in Computer Graphics

Interactive rigid body simulation is an important part of many modern computer tools, which no authoring tool nor game engine can do without. Such high‐performance computer tools open up new possibilities for changing how designers, engineers, modelers and animators work with their design problems. This paper is a self contained state‐of‐the‐art report on the physics, the models, the numerical methods and the algorithms used in interactive rigid body simulation all of which have evolved and matured over the past 20 years. Furthermore, the paper communicates the mathematical and theoretical details in a pedagogical manner. This paper is not only a stake in the sand on what has been done, it also seeks to give the reader deeper insights to help guide their future research.     

Adhesion Effects of Intermediate Layers on the Densification of Ceramic Powders

In the ceramic technology the first step to produce sintered bodies is the manufacturing of powders which then are densified. The adhesion mechanisms between the single particles and the agglomerates produced from them determine the densification process. Starting from theoretical considerations adhesion mechanisms, such as solid bridge formation, adhesive bonding and glide-promoting effects, are discussed in principle. Subsequently, the effects of surface-active substances on the densification behaviour of clay-ceramics and oxide-ceramic bodies are discussed. Further, the evaluation of the action of additives to the powder mixtures on the microstructure of the compacts, such as porsity and texture, leads to a compaction equation which describes the transition from the powder pile to a densified green body.     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

热压氮化硅在1200℃的高温疲劳损伤

研究了热压氮化硅陶瓷的室温和高温力学性能及在１２００℃的高温疲劳损伤行为，发现材料的弹性模量、抗变强度与断裂韧性均随温度升高而下降，但在１０００℃以上降低最为显著。在１２００℃高温疲劳寿命与应力之间符合单对数线性关系经分析发现这种现象与失效的热激活过程有关。通过对实验数据，ＸＲＤ相结构、变形动力学过程和断口的微观分析证明，陶瓷高温疲劳失效机理为“杂质空穴复合作用机制”。对热压氮化硅来说，失效机理主     

Effect of competitive interference on the biosorption of lead(II) by Chlorella vulgaris

Batch experiments were carried out to asses the effect of Cu(II) and Zn(II) on the biosorption of lead(II) ions by non-living Chlorella vulgaris. The uptake of Pb(II) was examined for single, binary and ternary solutions at different initial concentrations and different pH values. The experimental results showed that the uptake increased with increasing pH from 3.0 to an optimum value of 5.0. The biosorption of Pb(II) was found to be adversely affected by the presence of Cu(II) ions, while Zn(II) ions seemed to have negligible effect on the process. The equilibrium data were fitted to four isotherm models: Langmuir, Freundlich, Sips and Dubinin–Radushkevich; the Sips isotherm gave the best fit for the data. Modeling of the controlling mechanisms indicated that both intrinsic kinetics and mass transfer played major roles in controlling the process. A new dimensionless parameter, Ψ, was defined to asses the relative contributions of the two mechanisms to the biosorption of lead(II). Mass transfer seemed to be the dominant mechanism at low initial lead(II) concentrations, while intrinsic kinetics dominates at high concentrations.     

Plastic deformation of ZnO thin films through edge and screw dislocation movements

Columnar wurtzite grains were formed in sputtered ZnO thin films deposited on a plastic polyethylene terephthalate substrate. Selected-area diffraction patterns reveal that the columnar grains in the sputtered films present two preferred growth planes, namely, the basal (0002) and prismatic (100) growth planes. The diffraction patterns obtained also confirm that the microstructure of sputtered indium tin oxide thin films is amorphous in nature. Tensile tests indicate that the fracture strain of the ZnO thin film occurs between 1.73% and 2.14%, while the fracture strain of the indium tin oxide thin film occurs between 0.24% and 0.67%. Thus, the fracture toughness of the sputtered ZnO thin film is greater than that of the sputtered indium tin oxide thin film. High-resolution transmission electron microscopic images demonstrate that edge and screw dislocations could be identified in the sputtered ZnO thin films. Moreover, edge and screw dislocation movements may, respectively, be observed in the basal- and prismatic-oriented ZnO columnar grains of the sputtered ZnO thin films. Our results indicate that movements of the edge and screw dislocations in the basal- and prismatic-oriented ZnO columnar grains account for the plastic deformation of the investigated ZnO thin films under tensile stress.