Using nonmetallic catalysts

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. 

Asymmetric Reduction of Ketones Using Nonmetallic Catalysts... 

All the different methods using nonmetallic catalysts are similar in terms of procedure they all require anhydrous conditions to obtain high enantiomeric excesses. However, the oxazaphosphinamide catalysts can give relatively high enantiomeric excess without all the precautions of reactions conducted under... 

Calcined dolomites are the most widely used nonmetallic catalysts for tar conversion in biomass gasification processes.626-631 They are relatively inexpensive and are considered disposable. However, they are not very robust and quickly undergo attrition in fluidized-bed reactors. Consequently, dolomites find most use in fixed-bed catalytic reactors. Tar conversion efficiency is high when calcined dolomites are operated at high temperatures (900°C) with steam. Olivine, another naturally occurring mineral, has also demonstrated tar conversion activity similar to that of calcined dolomite. Olivine is a much more... 

Attempts to use nonmetallic catalysts for the catalysis of the oxygen reduction reaction in acid solutions have been unsuccessful. Tungsten-sodium bronzes or tungsten oxides, when used for this purpose, have to be... 

Appreciable interest was stirred by the sucessful use of nonmetallic catalysts such as oxides and organic metal complexes in electrochemical reactions. From 1968 on, work on the development of electrocatalysts on the basis of the mixed oxides of titanium and ruthenium led to the fabrication of active, low-wear electrodes for anodic chlorine evolution which under the designation dimensionally stable anodes (DSA) became a workhorse of the chlorine industry. 

Of considerable interest was the demonstration that metalloporphyrins and the like can be used as nonmetallic catalysts in electrochemical reactions, nourishing hopes that in the future, expensive platinum catalysts could be replaced. Starting in 1968, dimensionally stable electrodes with a catalyst prepared from the mixed oxides of titanium and ruthenium found widespread use in the chlorine industry. 

In the field of nonmetallic catalysts, particularly of oxides, Hauffe and co-workers (14a) used only semiconductors for which information concerning electronic and ion defects was available from measurements of electrical conductivity, thermoelectric properties, and Hall effect. These workers obtain a quantitative correlation between the reaction rate, the amount of chemisorption, and the number of electron defects of the catalysts. Since every catalyzed reaction is initiated by a chemisorption process involving one or several of the reacting gases, and because the nature of this chemisorption process determines the subsequent steps of the reaction, it seems appropriate to begin with a discussion of the mechanism of chemisorption. 

A detailed description of a chromia-on-alumina catalyst prepared by impregnation has been given elsewhere . Another supported nonmetallic catalyst widely used commercially is cobalt molybdate-on-alumina. The preparation of this catalyst using an alumina support with controlled pore-size distribution is as follows. Silica-stabilized alumina, with greater than 50% of its surface area in 3-8 nm pores and at least 3% of the total pore volume in pores greater than 200 nm in diameter, is impregnated with an aqueous solution of cobalt and molybdenum. The finished oxysulfide catalyst was tested for hydrodesulfurization of petroleum residuum at 370°C and 100 atm for 28 days and compared with a convential cobalt-molybdate catalyst having a major portion of the surface area in 3-7 nm pores. The latter catalyst and controlled pore catalyst maintained 57 and 80% activity, respectively. 

The use of mediators to improve reactivity or selectivity in nitrone cycloaddition chemistry begins with the nitrone generation step. As is well known, the N-alkyla-tion of oximes provides one of the most direct and convenient synthetic routes to N-alkylated nitrones from readily available aldehydes and ketones. Electrophilic mediators have been employed to activate alkenes for N-alkylation, both in intramolecular and intermolecular reactions. They include activation of the internal alkene function by the action of (a) strong nonmetallic electrophiles such as phenyl-selenenyl sulfate (159), and (b) metallic catalysts such as Ag(I) (160) and Pd(II) ions... 

Method of preparing random poly(amide-fe-ester) derivatives through depoly merization/repolymerization of cyclic polyesters then coreacting with lactam derivatives using a nonmetallic carbene catalyst This method for preparing polyester amides is unreported. 

The cleaning of the various catalyst samples has to be scrutinized for each material studied. For iron for example, the major impurity is sulfur, and its removal must be carried out outside the vacuum system in a furnace in a constant hydrogen flow for a long period of time (days). Trace metallic impurities or nonmetallic impurities may be removed either by argon ion bombardment in the vacuum chamber or by chemical treatment using gas-surface interactions of different types. 

Heterogeneous catalytic processes can often be intensified by the use of monolithic catalysts (39). These are metallic or nonmetallic bodies forming a multitude of straight, narrow channels of defined uniform cross-sectional shapes (Figure 13). In order to ensure sufficient porosity and to enhance the catalytically active surface, the inner walls of the monolith channels are usually covered with a thin layer of washcoat, which acts as the support for the catalytically active species. 

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