Platinum catalytic property

Two problems are directly related to electrocatalysis, i.e., to increase the overall rate of the reaction of electro-oxidation of methanol together with a reduction of the amount of platinum (and more generally of precious metals) in the electrode catalytic layer, and to improve the activity at low potentials by adding one or more other metals to modify the platinum catalytic properties. 

Usually they are employed as porous pellets in a packed bed. Some exceptions are platinum for the oxidation of ammonia, which is in the form of several layers of fine-mesh wire gauze, and catalysts deposited on membranes. Pore surfaces can be several hundred mVg and pore diameters of the order of 100 A. The entire structure may be or catalytic material (silica or alumina, for instance, sometimes exert catalytic properties) or an active ingredient may be deposited on a porous refractory carrier as a thin film. In such cases the mass of expensive catalytic material, such as Pt or Pd, may be only a fraction of 1 percent. 

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. 

A novel chiral dissymmetric chelating Hgand, the non-stabiUzed phosphonium ylide of (R)-BINAP 44, allowed in presence of [Rh(cod)Cl]2 the synthesis of a new type of eight-membered metallacycle, the stable rhodium(I) complex 45, interesting for its potential catalytic properties (Scheme 19) [81]. In contrast to the reactions of stabihzed ylides with cyclooctadienyl palladium or platinum complexes (see Scheme 20), the cyclooctadiene is not attacked by the carbanionic center. Notice that the reactions of ester-stabilized phosphonium ylides of BINAP with rhodium(I) (and also with palladium(II)) complexes lead to the formation of the corresponding chelated compounds but this time with an equilibrium be-... 

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. 

It was found in the 1960s that disperse platinum catalyst supported by certain oxides will in a number of cases be more active than a similar catalyst supported by carbon black or other carbon carrier. At platinum deposits on a mixed carrier of WO3 and carbon black, hydrogen oxidation is markedly accelerated in acidic solutions (Hobbs and Tseung, 1966). This could be due to a partial spillover of hydrogen from platinum to the oxide and formation of a tungsten bronze, H WOj (0 < a < 1), which according to certain data has fair catalytic properties. 

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. 

To the contrary, mnlticomponent nonmetallic systems such as mixed oxides often provide the possibility for a smooth or discontinuous variation of electrophysical parameters, and thns for some adjustment of their catalytic properties. In a number of cases, one can do without expensive platinum catalysts, instead using nonmetallic catalysts. Serious research into the properties of nonmetallic catalytic electrodes was initiated in the 1960s in connection with broader efforts to realize various kinds of fuel cells. 

The catalytic properties of a Pt/Sn combination were observed on different kinds of electrode materials alloys [90], electro co-deposits of Pt and Sn [89, 90], underpotential deposited tin [42] or a mixture of tin oxide and platinum deposited on glass [95], All different materials present a marked influence on methanol electrooxidation. 

Rare, shiny, and lightest metal of the platinum group. Hardens platinum and palladium. The presence of 0.1 % of ruthenium in titanium improves its resistance to corrosion 100-fold. The spectacular catalytic properties of ruthenium are used on industrial scales (hydrogenations, sometimes enan-tioselective, and metathesis). Titanium electrodes coated with ruthenium oxide are applied in chlorine-alkaline electrolysis. Suitable for corrosion-resistant contacts and surgical instruments. 

The method of metal introduction should significantly affect the degree of proximity between the Pt and acidic sites, hence the catalytic properties. In a previous study, the behavior of Pt/MCM-22 samples in n-hexane transformation was explored by Martins et al. [11]. In this study the same reaction was used in order to evaluate the influence of the mode of Pt introduction. Three 1 wt.% Pt/MCM-22 samples were prepared, differing by the mode of platinum introduction ion exchange, incipient wetness impregnation or mechanical mixture of the zeolite with Pt/Al203. 

Durable changes of the catalytic properties of supported platinum induced by microwave irradiation have been also recorded [29]. A drastic reduction of the time of activation (from 9 h to 10 min) was observed in the activation of NaY zeolite catalyst by microwave dehydration in comparison with conventional thermal activation [30]. The very efficient activation and regeneration of zeolites by microwave heating can be explained by the direct desorption of water molecules from zeolite by the electromagnetic field this process is independent of the temperature of the solid [31]. Interaction between the adsorbed molecules and the microwave field does not result simply in heating of the system. Desorption is much faster than in the conventional thermal process, because transport of water molecules from the inside of the zeolite pores is much faster than the usual diffusion process. 

It is important to compare the catalytic properties of Prussian blue with known hydrogen peroxide transducers. Table 13.2 presents the catalytic parameters, which are of major importance for analytical chemistry selectivity and catalytic activity. It is seen that platinum, which is still considered as the universal transducer, possesses rather low catalytic activity in both H202 oxidation and reduction. Moreover, it is nearly impossible to measure hydrogen peroxide by its reduction on platinum, because the rate of oxygen reduction is ten times higher. The situation is drastically improved in case of enzyme peroxidase electrodes. However, the absolute records of both catalytic activity... 

The SHE also utilizes the catalytic properties of platinum, so the electrode monitoring the energy of the H" " H2 couple is made of platinum coated with platinum black. Platinum black is a layer of finely divided Pt metal, which catalytically speeds up the dissociation and association of H-H molecules. The catalysis here aids the speed at which equilibration is attained so that the measurement is more likely to be performed reversibly. 

The group 10 metals, such as palladium and platinum, are active for the conversion of methanol. However, they are much less selective than the copper-based catalysts, yielding primarily the decomposition products [123,124,133]. This catalytic property makes them less feasible for fuel cell applications. The only exception found is for Pd/ZnO, which showed selectivity close to that of a copper catalyst [105, 121]. 

The commercial applications of osmium are limited and considerably fewer than other platinum group metals. Its aUoys are very hard and are used to make tips of fountain-pen nibs, phonograph needles, and pivots. The metal also exhibits effective catalytic properties in hydrogenation and other organic reactions. Such catalytic apphcations, however, are limited and osmium fads to replace other noble metals, particularly paUadium and platinum, which are more effective as catalysts and cost less. 

He was the first to observe the very stable adsorbed monatomic hints on tungsten and platinum filaments, and was able, alter experiments with oil films on water, lo formulaic a general theory ol adsorbed films. He also studied the catalytic properties of such films. 

The standard regeneration treatment described in the experimental section appeared to be necessary to recover the catalytic properties of the platinum surface. 

The carbides and nitrides of the early transition metals have attracted considerable attention. Much of this can be attributed to the catalytic properties of these materials. Levy and Boudart1 were the first to note the Pt-like catalytic behavior of WC, which for many reactions is more catalytically active than metallic tungsten.2 Others have noted that the early transition metal carbides and nitrides, in general, are excellent catalysts for reactions characteristic of the more expensive noble metals.3,4 For example, WC has been found to catalyze the isomerization of neopentane to isopentane,1 a reaction that previously had been known to be catalyzed only by iridium and platinum.5... 

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