Catalysts, nonmetallic

In electrochemical systems, many restrictions exist in the use of metal catalysts. Most metals other than the expensive noble metals are unstable at anodic potentials and cannot be nsed for anodic processes. The catalytic activity and selectivity of metal catalysts basically are determined by their chemical nature and are rarely open to adjustments. 

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. 

Among the carbon materials, different types of graphite have long been nsed in a number of technical electrochemical processes (e.g., as anodes in electrochemical 

Other types of carbon (amorphous or transitional forms with turbostratic structure) consist of fragments of graphitelike regions cross-linked to a three-dimensional polymer by carbon chains. Unlike graphite, the transitional forms are organic semiconductors with electrical properties determined by delocalized rr-electrons. 

In electrocatalysis, the activated carbons, glassy carbon, and carbon black are the transitional forms used. Carbon black is the product of incomplete combustion or decomposition of organic compounds. The shape of its particles is close to spherical. They contain several carbon atom lattice fragments arranged without order. Various types of carbon black serve as substrates for metal catalysts, the properties of the carbon blacks themselves having a strong elfect on the catalytic activity of the combined catalysts thus obtained. 

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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. 

METAL - AIR BATTERIES WITH CARBONACEOUS AIR ELECTRODES AND NONMETALLIC CATALYSTS... 

Asymmetric catalytic reduction reactions represent one of the most efficient and convenient methods to prepare a wide range of enantiomerically pure compounds (i.e. a-amino acids can be prepared from a-enamides, alcohols from ketones and amines from oximes or imines). The chirality transfer can be accomplished by different types of chiral catalysts metallic catalysts are very efficient for the hydrogenation of olefins, some ketones and oximes, while nonmetallic catalysts provide a complementary method for ketone and oxime hydrogenation. 

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... 

Table 11.4 Catalytic reduction of ketones by nonmetallic catalysts (results according to the relevant publications).

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. 

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... 

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