Surface properties catalytic activity

The properties of siloxide as ancillary ligand in the system TM-O-SiRs can be effectively utilized in molecular catalysis, but predominantly by early transition metal complexes. Mono- and di-substituted branched siloxy ligands (e.g., incompletely condensed silsesquioxanes) have been employed as more advanced models of the silanol sites on silica surface for catalytically active centers of early TM (Ti, W, V) that could be effectively used in polymerization [5], metathesis [6] and epoxidation [7] of alkenes as well as dehydrogenative coupling of silanes [8]. 

Owing to the possibility of tuning (1) their acidic and basic properties, (2) their surface hydrophilicity, and (3) their adsorption and shape-selectivity properties, catalytic activity of zeolites was investigated in the production of HMF from carbohydrates. Whatever the hexose used as starting material, acidic pillared montmorillonites and faujasite were poorly selective towards HMF, yielding levu-linic and formic acids as the main products [81-83]. 

Synthesis and preparation process affects some properties of ceria-based materials such as formed phase, particle size, surface area, catalytic activities, and OSC etc. Therefore, many studies on synthesis, preparation, and modification have been carried out to develop the ceria-based materials of high catcilytic aetivities, OSC, and thermal durability. In this chapter, conventional processes and recent advances in the synthesis and modification of the ceria-based materials are reviewed with the dependence of these methods on the characteristics of the materials. 

The activity of the catalyst samples for both hydration reactions depends strongly on Nai. For high framework aluminium contents (from 50, corresponding to the parent H-Y, to about 35) the catalyst samples are inactive. This is probably due to the hydrophilic properties of the zeolite s active surface. The catalytic activity increases with the framework dealumination to reach a maximum value at Nm = 22. This increase is likely to be due not only to the increase in the acid strength of the Bronsted sites, but also to the changing in the hydrophilic/hydrophobic balance of the zeolite s active surface. 

The deactivation of three way catalysts (TWC) can be studied by the determination of the change of some of their properties such as specific surface area, catalytic activity or precious metal dispersion. Two qualitative and quantitative methods have been investigated in order to characterize TWC oxygen species Temperature Programmed Desorption (O2 TPD) and Temperature Programmed Reduction in hydrogen (H2 TPR). 

It turned out that the dodecylsulfate surfactants Co(DS)i Ni(DS)2, Cu(DS)2 and Zn(DS)2 containing catalytically active counterions are extremely potent catalysts for the Diels-Alder reaction between 5.1 and 5.2 (see Scheme 5.1). The physical properties of these micelles have been described in the literature and a small number of catalytic studies have been reported. The influence of Cu(DS)2 micelles on the kinetics of quenching of a photoexcited species has been investigated. Interestingly, Kobayashi recently employed surfactants in scandium triflate catalysed aldol reactions". Robinson et al. have demonshuted that the interaction between metal ions and ligand at the surface of dodecylsulfate micelles can be extremely efficient. ... 

The typical industrial catalyst has both microscopic and macroscopic regions with different compositions and stmctures the surfaces of industrial catalysts are much more complex than those of the single crystals of metal investigated in ultrahigh vacuum experiments. Because surfaces of industrial catalysts are very difficult to characterize precisely and catalytic properties are sensitive to small stmctural details, it is usually not possible to identify the specific combinations of atoms on a surface, called catalytic sites or active sites, that are responsible for catalysis. Experiments with catalyst poisons, substances that bond strongly with catalyst surfaces and deactivate them, have shown that the catalytic sites are usually a small fraction of the catalyst surface. Most models of catalytic sites rest on rather shaky foundations. 

The catalytic properties of the shock-modified rutile whose defect properties have been reported in previous sections of this chapter have been studied in a flow reactor used to measure the oxidation of CO by Williams and coworkers [82G01, 86L01]. As shown in Fig. 7.7 the effect of shock activation is substantial. Whereas the unshocked material displays such low activity that an effect could only be observed at the elevated temperature of 400 °C, the shock-modified powder shows substantially enhanced catalytic activity with the extent of the effect depending on the shock pressure. After a short-time transient is annealed out, the activity is persistent for about 8 h. Although the source of the surface defects that cause the activity is not identified, the known annealing behavior of the point defects indicates that they are not responsible for the effect. 

A short survey of information on formation, structure, and some properties of palladium and nickel hydrides (including the alloys with group IB metals) is necessary before proceeding to the discussion of the catalytic behavior of these hydrides in various reactions of hydrogen on their surface. Knowledge of these metal-hydrogen systems is certainly helpful in the appreciation, whether the effective catalyst studied is a hydride rather than a metal, and in consequence is to be treated in a different way in a discussion of its catalytic activity. 

We start by considering a schematic representation of a porous metal film deposited on a solid electrolyte, e.g., on Y203-stabilized-Zr02 (Fig. 5.17). The catalyst surface is divided in two distinct parts One part, with a surface area AE is in contact with the electrolyte. The other with a surface area Aq is not in contact with the electrolyte. It constitutes the gas-exposed, i.e., catalytically active film surface area. Catalytic reactions take place on this surface only. In the subsequent discussion we will use the subscripts E (for electrolyte) and G (for gas), respectively, to denote these two distinct parts of the catalyst film surface. Regions E and G are separated by the three-phase-boundaries (tpb) where electrocatalytic reactions take place. Since, as previously discussed, electrocatalytic reactions can also take place to, usually,a minor extent on region E, one may consider the tpb to be part of region E as well. It will become apparent below that the essence of NEMCA is the following One uses electrochemistry (i.e. a slow electrocatalytic reaction) to alter the electronic properties of the metal-solid electrolyte interface E. 

The recovery of petroleum from sandstone and the release of kerogen from oil shale and tar sands both depend strongly on the microstmcture and surface properties of these porous media. The interfacial properties of complex liquid agents—mixtures of polymers and surfactants—are critical to viscosity control in tertiary oil recovery and to the comminution of minerals and coal. The corrosion and wear of mechanical parts are influenced by the composition and stmcture of metal surfaces, as well as by the interaction of lubricants with these surfaces. Microstmcture and surface properties are vitally important to both the performance of electrodes in electrochemical processes and the effectiveness of catalysts. Advances in synthetic chemistry are opening the door to the design of zeolites and layered compounds with tightly specified properties to provide the desired catalytic activity and separation selectivity. 

This is because the heat capacity of a wall of finite thickness is several orders of magnitude higher than that of the hot combustion products. However, some researchers did observe a small effect of the properties of the wall [17] on the quenching distance. This was interpreted in terms of some residual catalytic activity of the wall surface, poisoned by the combustion products from the preceding experiments [18]. With respect to this explanation, the surface of any material moistened through the condensation of the water vapor produced in the reaction is supposed to have very similar, low activity. 

In this contribution it is shown that local density functional (LDF) theory accurately predicts structural and electronic properties of metallic systems (such as W and its (001) surface) and covalently bonded systems (such as graphite and the ethylene and fluorine molecules). Furthermore, electron density related quantities such as the spin density compare excellently with experiment as illustrated for the di-phenyl-picryl-hydrazyl (DPPH) radical. Finally, the capabilities of this approach are demonstrated for the bonding of Cu and Ag on a Si(lll) surface as related to their catalytic activities. Thus, LDF theory provides a unified approach to the electronic structures of metals, covalendy bonded molecules, as well as semiconductor surfaces. 

Cu and Ag on Si(lll) surfaces. In the last example, we come back to surfaces. It is well known (44-46) that Cu catalyzes the formation of dimethyl-dichlorosilane from methylchloride and solid silicon, which is a crucial technological step in the synthesis of silicone polymers. Even today, the details of the catalytic mechanism are unclear. Cu appears to have unique properties for example, the congener Ag shows no catalytic activity. Thus, the investigation of the differences between Cu and Ag on Si surfaces can help in understanding the catalytic process. Furthermore, the bonding of noble metal atoms to Si surfaces is of great importance in the physics and chemistry of electronic devices. 

The next level is that of small catalytically active particles, with typical dimensions of between 1 and 10 nm, and inside the pores of support particles (pm range). The questions of interest are the size, shape, structure and composition of the active particles, in particular of their surfaces, and how these properties relate to catalytic reactivity. Although we will deal with heterogeneous catalysis, the anchoring of catalytic... 

Abstract This review is a summary of supported metal clusters with nearly molecular properties. These clusters are formed hy adsorption or sirnface-mediated synthesis of metal carbonyl clusters, some of which may he decarhonylated with the metal frame essentially intact. The decarhonylated clusters are bonded to oxide or zeolite supports by metal-oxygen bonds, typically with distances of 2.1-2.2 A they are typically not free of ligands other than the support, and on oxide surfaces they are preferentially bonded at defect sites. The catalytic activities of supported metal clusters incorporating only a few atoms are distinct from those of larger particles that may approximate bulk metals. 

A general problem existing with all multicomponent catalysts is the fact that their catalytic activity depends not on the component ratio in the bulk of the electrode but on that in the surface layer, which owing to the preferential dissolution of certain components, may vary in time or as a result of certain electrode pretreatments. The same holds for the phase composition of the surface layer, which may well be different from that in the bulk alloy. It is for this reason that numerous attempts at correlating the catalytic activities of alloys and other binary systems with their bulk properties proved futile. 

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