Metal surfaces catalytic properties

In addition to modification of surfaces by non-metals, the catalytic properties of metals can also be altered greatly by the addition of a second transition metaP ". Interest in bimetallic catalysts has arisen steadily over the years because of the commercial success of these systems. This success results from an enhanced ability to control the catalytic activity and selectivity by tailoring the catalyst composition . A long-standing question regarding such bimetallic systems is the nature of the properties of the mixed-metal system which give rise to its enhanced catalytic performance relative to either of its individual metal components. These enhanced properties (improved stability, selectivity and/or activity) can be accounted for by one or more of several possibilities. First, the addition of one metal to a second may lead to an electronic modification of either or both of the metal constituents. This... 

The modification of surface catalytic properties by the deposition of metal adatoms has been studied extensively in the field of electrocatalysis 45-59 The main and common metals used as adatoms have low energy of adsorption (see Figure 21.2). Adatoms are considered as a means to enhance the catalytic activity of the electrode surface. Underpotential deposition is the process of the deposition of submonolayer amounts of metal ions (Mz+) on an inert foreign metal (M) support from a solution considered at more positive potentials than the corresponding Mz+/M equilibrium potential. 

There are other types of active sites. In 1955 Kobozev (17) pointed out that sometimes—especially with certain metals—the catalytic properties could be due to the properties of atoms, but that in other cases—as with some metal oxides—the catalytic property might be associated with the entire crystal We showed later (j ) that in at least one case, silica-alumina catalyst, it is very easy to err concerning the nature of the site Thus, evidence for Bronsted acidity could be interpreted as evidence for the presence of aluminum which can be ion-exchanged when the catalyst is placed in salt solution Looking at all these examples, we conclude that that there are many different sources of activity on the solid catalyst surface. 

The growth of solid films onto solid substrates allows for the production of artificial stmctures that can be used for many purposes. For example, film growth is used to create pn junctions and metal-semiconductor contacts during semiconductor manufacture, and to produce catalytic surfaces with properties that are not found in any single material. Lubrication can be applied to solid surfaces by the appropriate growth of a solid lubricating film. Film growth is also... 

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

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. 

Catalysis by Metals. Metals are among the most important and widely used industrial catalysts (69,70). They offer activities for a wide variety of reactions (Table 1). Atoms at the surfaces of bulk metals have reactivities and catalytic properties different from those of metals in metal complexes because they have different ligand surroundings. The surrounding bulk stabilizes surface metal atoms in a coordinatively unsaturated state that allows bonding of reactants. Thus metal surfaces offer an advantage over metal complexes, in which there is only restricted stabilization of coordinative... 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

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. 

Ruthenium-copper and osmium-copper clusters (21) are of particular interest because the components are immiscible in the bulk (32). Studies of the chemisorption and catalytic properties of the clusters suggested a structure in which the copper was present on the surface of the ruthenium or osmium (23,24). The clusters were dispersed on a silica carrier (21). They were prepared by wetting the silica with an aqueous solution of ruthenium and copper, or osmium and copper, salts. After a drying step, the metal salts on the silica were reduced to form the bimetallic clusters. The reduction was accomplished by heating the material in a stream of hydrogen. 

The results of the EXAFS studies on osmium-copper clusters lead to conclusions similar to those derived for ruthenium-copper clusters. That is, an osmium-copper cluster Is viewed as a central core of osmium atoms with the copper present at the surface. The results of the EXAFS investigations have provided excellent support for the conclusions deduced earlier (21,23,24) from studies of the chemisorption and catalytic properties of the clusters. Although copper is immiscible with both ruthenium and osmium in the bulk, it exhibits significant interaction with either metal at an interface. 

From the previous results, it has been proven that the nature of the support, although it has no significant influence on the Pd electronic properties, modifies the catalytic properties of the solids To permit a better understanding of these supports effects, the surface properties of the supports (in the presence of the metal) have been studied, in particular the acidic properties and the oxygen mobilities. The A1203 and Z1O2 supports have been mainly onsidered. 

Surface composition and structure of bimetallic nanoparticles are crucially important for their catalytic property as well as their optical property. IR measurement of CO adsorbed on surface metals (CO-IR) is utilized for this purpose. CO is adsorbed on metals not only on-top sites but also in two-fold or three-fold sites, depending on the kinds of metals and their surface structures. The dramatical changes of wavenumber of adsorbed CO occurs depending on the binding structure [177-181]. 

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