Metal oxides, catalytic properties

Analagously to metal oxides, the properties of metals change when the soUd is constituted by particles and the size of these particles enters the nanomehic regime. Relevant to this chapter is the catalytic activity of gold nanoparticles, a... 

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. 

Nobel metal based catalysts such as Pt, Pd, Rh and Ir has been reported to exhibit considerable activities in this process [3-4], Because of higher activities Pd and Pt based catalysts are most widely used, however Pd based catalysts have been reported to be catalytically more active than Pt in this process and therefore most of the recent researches have focused on Pd as the active component [5-7], As a matter of fact, properties of the metal oxide catalytic supports also play an important role in the catalytic processes. 

The methods for miniaturization of chemical and biosensors are based on an extension of VLSI fabrication techniques, however with a broader range of materials [1-6], The range of materials is beyond what is normal for IC electronic devices because additional functionality is needed. These materials include electrochemi-cally active metals with catalytic properties, conductive oxides, and high-temperature materials. Examples of metal oxides include Sn02, WO3, and Ti02, and other catalytic metals include Pt, Ru, Ir, Pd, and Ag needed for electrochemical sensors [7,8]. As the dimensions of semiconductor devices continue to move to smaller gate lengths, nanoscale fabrication techniques are now developed. Hence, stmctures for sensors... 

Oxidation can also occur at the central metal atom of the phthalocyanine system (2). Mn phthalocyanine, for example, can be produced ia these different oxidation states, depending on the solvent (2,31,32). The carbon atom of the ring system and the central metal atom can be reduced (33), some reversibly, eg, ia vattiag (34—41). Phthalocyanine compounds exhibit favorable catalytic properties which makes them interesting for appHcations ia dehydrogenation, oxidation, electrocatalysis, gas-phase reactions, and fuel cells (qv) (1,2,42—49). 

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. 

Changes in the composition of gaseous products as reaction proceeds may make definition of the fractional decomposition, a, difficult. For example, product CO and residual carbon may be capable of reducing a metallic oxide, particularly at high a and the catalytic properties of an accumulating solid product may result in promotion of secondary gas reactions. 

Kadlec and Rosmusova [1153] believe that both Ni and Co oxalates initially yield product oxide and that the proportion of metal increases with a. Since nickel oxalate decomposes at temperatures 60 K lower than those for CoC204, even a small proportion of Ni2+ markedly increases the rate of decomposition of cobalt oxalate. The effect was attributed to the catalytic properties of the preferentially formed Ni metal. The a—time curves were generally sigmoid and showed only slight deviations in shape with changes in the Ni Co ratio. In the decomposition of a mechanical... 

In all these cases the support has a dramatic effect on the activity and selectivity of the active phase. In classical terminology all these are Schwab effects of the second kind where an oxide affects the properties of a metal. Schwab effects of the first kind , where a metal affects the catalytic properties of a catalytic oxide, are less common although in the case of the Au/Sn02 oxidation catalysts9,10 it appears that most of the catalytic action takes place at the metal-oxide-gas three phase boundaries. 

In Chapter 1 we emphasized that the properties of a heterogeneous catalyst surface are determined by its composition and structure on the atomic scale. Hence, from a fundamental point of view, the ultimate goal of catalyst characterization should be to examine the surface atom by atom under the reaction conditions under which the catalyst operates, i.e. in situ. However, a catalyst often consists of small particles of metal, oxide, or sulfide on a support material. Chemical promoters may have been added to the catalyst to optimize its activity and/or selectivity, and structural promoters may have been incorporated to improve the mechanical properties and stabilize the particles against sintering. As a result, a heterogeneous catalyst can be quite complex. Moreover, the state of the catalytic surface generally depends on the conditions under which it is used. 

While the discovery of the catalytic properties of zeolites was driven by the desire to improve industrial prcKessing, the development of emission control catalysts was necessitated by governmental fiat. The first requirement was for 90+% removal of CO and of hydrocarbons, a goal which could not be met by oxidation with base metal oxides. To achieve the required spedfications during automobile operations, it was necessary to develop supported platinum catalysts. Originally the support was alumina in pellet form. Later platinum on cordierite was used in honeycomb form, containing 200-400 square channels per square inch. 

Oxide- and Zeolite-supported "Molecular" Metal Clusters Synthesis, Structure, Bonding, and Catalytic Properties... 

Gates BC (2005) Oxide- and Zeolite-supported Molecular Metal Clusters Synthesis, Structure, Bonding, and Catalytic Properties. 16 211-231 Gibson SE (nee Thomas), Keen SP (1998) Cross-Metathesis. 1 155-181 Gisdakis P, see Rosch N (1999) 4 109-163 Gdrling A, see Rosch N (1999) 4 109-163... 

Adatoms produce a strong change in catalytic properties of the metal on which they are adsorbed. These catalytic effects are highly specific. They depend both on the nature of the metal and on the nature of the adatoms they also depend on the nature of the electrochemical reaction. For instance, tin adatoms on platinum strongly (by more than two orders of magnitude) enhance the rate of anodic methanol oxidation. 

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