Heterogeneous solid oxides

Heterogeneous Solid Oxides, Alloys, and Related Materials... 

Table 3.1 lists some of the anodic reactions which have been studied so far in small cogenerative solid oxide fuel cells. A more detailed recent review has been written by Stoukides46 One simple and interesting rule which has emerged from these studies is that the selection of the anodic electrocatalyst for a selective electrocatalytic oxidation can be based on the heterogeneous catalytic literature for the corresponding selective catalytic oxidation. Thus the selectivity of Pt and Pt-Rh alloy electrocatalysts for the anodic NH3 oxidation to NO turns out to be comparable (>95%) with the... 

A brief summary of current and potential processes is given in Table 8.1. As shown in the table, most of the reactions are hydrolysis, hydrogenolysis, hydration, hydrogenation, oxidation, and isomerization reactions, where catalysis plays a key role. Particularly, the role of heterogeneous catalysts has increased in this connection in recent years therefore, this chapter concerns mostly the application of heterogeneous solid catalysts in the transformation of biomass. An extensive review of various chemicals originating from nature is provided by Maki-Arvela et al. [33]. 

In heterogeneous solid-state reactions where the composition of both solid reactants does not change, the electrode s eqnilibrinm potential depends only on the nature of the two phases, not on their relative amonnts. Hence, dnring the reaction the potential does not change. It also remains constant when the cnrrent is interrupted after partial reduction or oxidation. 

This mechanism is of fundamental importance in the understanding of solid-state heterogeneous catalytic oxidation processes. The glide defect regions are... 

The transformation of alcohols to the corresponding carbonyl compounds or carboxylic acids is one of the few examples in which a heterogeneous (solid) catalyst is used in a selective, liquid phase oxidation (7,2). The process, which is usually carried out in an aqueous slurry, with supported platinum or palladium catalysts and with dioxygen as oxidant, has limited industrial application due to deactivation problems. 

A proper description of heterogeneously catalyzed oxidation reactions must treat several difficult problems simultaneously. First is the characterization of the solid surface in its reactive state. What oxygen species exist on this surface and what reactions does each species undergo What other sites for adsorption are present Second is the problem of reaction path. What steps are involved in the reaction What are the structures and relative energy contents of the intermediates Third is the problem of reaction velocity, a general and difficult problem in all chemistry. What are transition states, activation energies, and reaction probabilities for the various steps ... 

Fig. 1.6 Illustration of a planar-stack, solid-oxide fuel cell (SOFC), where an membrane-electrode assembly (MEA) is sandwiched between an interconnect structure that forms fuel and air channels. There is homogeneous chemical reaction within the flow channels, as well as heterogeneous cehmistry at the channel walls. There are also electrochemical reactions at the electrode interfaces of the channels. A counter-flow situation is illustrated here, but co-flow and cross-flow configurations are also common. Channel cross section dimensions are typically on the order of a millimeter.

Metal oxidation is a heterogeneous solid state reaction and starts in the same way as other heterogeneous reactions with nucleation and initial growth. This was discussed in Chapter 6. A time-dependent nucleation rate may dominate the overall growth kinetics of thin Films. Even under an optical microscope (i.e., in macroscopic dimensions), preferential sites of growth can still be discerned [J. Benard (1971)). This indicates that lateral transport on the surface (e.g., at sites where screw dislocations emerge) can possibly be more important for the initial reactive growth than transport across thin oxide layers. 

The foregoing classification is not without ambiguity. For example, it is common practice to call the reaction A - B +C° (see Fig. 6-1) induced by decreasing the temperature a phase transformation. The similar (peritectoid) reaction C = a+fi (Fig. 12-2) induced by a temperature increase, however, is named a decomposition reaction. In addition, the isothermal reaction AO = A+j02, which occurs if the intensive variable fio2 is decreased so that AO decomposes, is called a metal oxide reduction. It is thus categorized as a genuine heterogeneous solid state reaction (the... 

Metal carbonates are often used as reagents in solid-state reactions because heating them creates finely divided metal oxides as a result of the release of C02(g) from the crystal lattice. These finely divided particles, which are made freshly in situ, are often more reactive in heterogeneous solid-state reactions than are the metal oxides found on the laboratory shelf because they have a higher surface area that is more reactive because of its fresh preparation. Determine the minimum temperature necessary to achieve spontaneous thermal decomposition of BaC03. 

Elements of /< greater than 3.2 form simple metallate anions in solutions of high pH—i.e., strongly alkaline solutions. As the pH of such solutions is lowered, isopolyanions are produced in many cases, ultimately yielding hydrous oxides, or salts of isopolymetallate ions as heterogeneous solid phases. Again, many of the isopolyanions exhibit buffer capacity. 

Solid acid catalysts such as mixed oxides (chalcides) have been used extensively for many years in the petroleum industry and organic synthesis. Their main advantage compared with liquid acid catalysts is the ease of separation from the reaction mixture, which allows continuous operation, as well as regeneration and reutilization of the catalyst. Furthermore, the heterogeneous solid catalysts can lead to high selectivity or specific activity. Due to the heterogeneity of solid superacids, accurate acidity measurements are difficult to carry out and to interpret. Up until now, the most useful way to estimate the acidity of a solid catalyst is to test its catalytic activity in well-known acid-catalyzed reactions. 

Gupta G.K., Dean A.M., Hecht E.S., Zhu H., Kee R.J. (2005) The influence of heterogeneous chemistry and electrochemistry on gas-phase moleculear-weight growth and deposit formation. In Solid Oxide Fuel Cells IX (SOFC-IX), Electrochemical Society Proceedings, Quebec PQ, 15-20 May, Vol. 1, Cells, Stacks, and Systems, S.C. Singhal and J. Mizusaki (Eds.), The Electrochemical Society, Pennington, NJ, pp. 679-688. 

Dibble, L. A. Raupp, G. B. Kinetics of the gas-solid heterogeneous photocatalytic oxidation of trichloroethylene by near UV illuminated T102, Catal. Let 1990,4,345. 

Heterogeneous or heterogenised catalysts (Appendix 2) are extensively used in the form of solid oxides for large industrial production (as shown in Section 5.2), but so far have not found significant uses in fine chemicals manufacture, although some attractive routes have been worked out. For... 

Heterogeneous solid propellants possess additional mechanisms with potentials for producing oscillatory burning. For example, certain metalized composite propellants have been observed to burn in the laboratory with identifiable ranges of frequencies of oscillation [118] in this case, the mechanism may involve chemical interactions between the metal and the oxidizer. It was indicated in Section 9.1.5.5 that heterogeneities introduce at least local periodicities and that, in the presence of a mechanism for synchronizing the phases of the oscillations over the surface of the propellant, sustained coherent oscillations of the combustion will occur. A review is... 

The possibility that an electron-transfer path is involved in photo-sensitized oxygenation has been considered on several occasions. This is relevant in several fields of application, from the biomimetic oxygenation of indole and flavin derivatives [106] to pollutant control. With reference to latter, it has been suggested that SET occurs in heterogeneous photosensitized oxidation by solid semiconductors, in which the adsorbed substrate donates an electron to the photogenerated hole and... 

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