Hydrocarbons, oxidation, catalysis mechanism

The third and last part of the book (Chapters 12-16) deals with zeolite catalysis. Chapter 12 gives an overview of the various reactions which have been catalyzed by zeolites, serving to set the reader up for in-depth discussions on individual topics in Chapters 13-16. The main focus is on reactions of hydrocarbons catalyzed by zeolites, with some sections on oxidation catalysis. The literature review is drawn from both the patent and open literature and is presented primarily in table format. Brief notes about commonly used zeolites are provided prior to each table for each reaction type. Zeolite catalysis mechanisms are postulated in Chapter 13. The discussion includes the governing principles of performance parameters like adsorption, diffusion, acidity and how these parameters fundamentally influence zeolite catalysis. Brief descriptions of the elementary steps of hydrocarbon conversion over zeolites are also given. The intent is not to have an extensive review of the field of zeolite catalysis, but to select a sufficiently large subset of published literature through which key points can be made about reaction mechanisms and zeolitic requirements. 

A redox mechanism for oxidation catalysis was proposed by Mars and van Krevelen (34) for the oxidation of aromatics over V205. This mechanism introduced the concept that lattice oxygen of a reducible metal oxide could serve as a useful oxidizing agent for hydrocarbons. Moreover, it formed the basis for the early work at SOHIO which led to the development of the bismuth molybdate catalyst. Since that time there have been many reports which support the redox concept. 

While the overall reaction of anthracene oxidation to form anthra-quinone as shown above involves the interaction of three atoms of oxygen per molecule of hydrocarbon, the actual mechanism of the catalysis is more or less obscure. From the observations of Senseman and Nelson86 the vanadium oxide catalysts function by being alternately reduced to a lower oxide by the hydrocarbon and oxidized to the pentoxide by the oxygen of the air used. Thus ... 

The catalytic activities of metals and semiconductors would be expected to differ due to their different electronic properties. However, under conditions of oxidation catalysis many metals become coated with a more or less thin semiconducting film of the given metal oxide, and this might be the reason why the mechanism of hydrocarbon oxidation on metals and semiconductors has much in common (59). 

Based on these observations and several other experimental results with cofeeding of ethene and 1-alkene,9 the selectivity of branched hydrocarbons,11 and the different promoter effects of Li-, Na-, K-, and Cs-carbonate/oxide,1213 a novel mechanism has been proposed that is consistent with these various experimental results.14 The formulation of this mechanism follows the knowledge of analogous reactions in homogeneous catalysis and gives a detailed insight in the crucial step of C-C linkage formation. The aim of this work is to discuss in detail these experiments and their relationship to the proposed mechanism. 

Cobalt bromide is used as a catalyst in the technology of production of arylcarboxylic acids by the oxidation of methylaromatic hydrocarbons (toluene, p-xylene, o-xylene, polymethyl-benzenes). A cobalt bromide catalyst is a mixture of cobaltous and bromide salts in the presence of which hydrocarbons are oxidized with dioxygen. Acetic acid or a mixture of carboxylic acids serves as the solvent. The catalyst was discovered as early as in the 1950s, and the mechanism of catalysis was studied by many researchers [195-214],... 

Metal oxides possess multiple functional properties, such as acid-base, redox, electron transfer and transport, chemisorption by a and 71-bonding of hydrocarbons, O-insertion and H-abstract, etc. which make them very suitable in heterogeneous catalysis, particularly in allowing multistep transformations of hydrocarbons1-8 and other catalytic applications (NO, conversion, for example9,10). They are also widely used as supports for other active components (metal particles or other metal oxides), but it is known that they do not act often as a simple supports. Rather, they participate as co-catalysts in the reaction mechanism (in bifunctional catalysts, for example).11,12... 

It is known that the oxidation of alkyl-substituted aromatic hydrocarbons in acetic acid on metal bromide catalysis follows the one-electron transfer mechanism (Sheldon and Kochi 1981). The rate-determining stage is the one-electron transfer from the substrate to the metal ion in the highest oxidation state (Digurov et al. 1986). As a result, an unstable cation-radical is formed that... 

Currently, low-temperature CO oxidation over Au catalysts is practically important in connection with air quality control (CO removal from air) and the purification of hydrogen produced by steam reforming of methanol or hydrocarbons for polymer electrolyte fuel cells (CO removal from H2). Moreover, reaction mechanisms for CO oxidation have been studied most extensively and intensively throughout the history of catalysis research. Many reviews [4,19-28] and highlight articles [12, 29, 30] have been published on CO oxidation over catalysts. This chapter summarizes of the state of art of low temperature CO oxidation in air and in H2 over supported Au NPs. The objective is also to overview of mechanisms of CO oxidation catalyzed by Au. 

In the current volume a variety of subjects is treated by competent authors. These subjects deal with new techniques of surface investigations with the microbalance, with the elucidation of reaction mechanisms by the concept of intermediates, and with specialized studies of the ammonia synthesis, hydrogenations, carbon monoxide oxidation and hydrocarbon syntheses. In addition, Volume V contains an extensive critical review of Russian literature in catalysis. 

Selective Oxidation and Ammoxidation of Propylene by Heterogeneous Catalysis Robert K. Grasselli and James D. Burrington Mechanism of Hydrocarbon Synthesis over Fischer-Tropsch Catalysts P. Biloen and W. M. H. Sachtler Surface Reactions and Selectivity in Electrocatalysis... 

One of the most intriguing reactions in the chytochrome P450 catalysis is the transfer of second electron and dioxygen activation, which appears to be a key step of the entire process. The chemical nature of reactive oxidizing species appears in the coordination sphere of heme iron and the mechanism of hydroxylation of organic compounds, saturated hydrocarbons in particular, is a much debated question in the field of the cytochrome P450 catalysis. To solve this problem, an entire arsenal of modern experimental and theoretical methods are employed. The catalytic pathway of cytochrome P450cam from Pseudomonas putida obtained on the basis of X-ray analysis at atomic resolution is presented in Fig. 3.10. 

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