Metal oxides, as heterogenous catalysts

The key issue in effective catalytic oxidation of organics is finding a suitable catalyst. Oxidation of aqueous phenol solutions by using different transition metal oxides as heterogeneous catalysts is already known [4-6]. On the other hand, the potential of molecular sieves to catalyze oxidative phenol destruction has not been examined yet. The objective of this contribution is to provide kinetic and mechanistic data on the catalytic liquid-phase oxidation of aqueous phenol solutions obtained in the presence of various transition metal oxides and molecular sieves. The reaction was studied in a semibatch slurry as well as two-and three-phase continuous-flow reactors. Another matter of concern was the chemical stability of catalysts under the reaction conditions. 

Harriman A, Pickering IJ, Thomas JM, Christensen PA (1988) Metal oxides as heterogeneous catalysts for oxygen evolution under photochemical conditions. J Chem Soc Faraday Trans 1 84 2795-2806... 

A number of factors are of common importance for the application of metal oxides as heterogeneous catalysts. These are as follows ... 

In current research work, mixed metal oxide based heterogeneous catalysts were prepared and employed for the triglyceride transesteriftcation as well as glycerol esterification reaction to produce triacetin and glycerol carbonate. 

All previously discussed examples of living cationic polymerization of vinyl ethers were based on homogeneous polymerization media. In 2007, Oashima and coworkers demonstrated the living polymerization of isobutyl vinyl ether in the presence of iron(III) oxide as heterogeneous catalyst and ethyl acetate or dioxane as base [58]. The major advantage of this heterogeneous catalytic system is the easy removal of the metal oxide catalyst. In addition, it was demonstrated that the iron(III) oxide could be reused for at least five times without a decrease in activity. 

E. Kemnitz and D. H. Menz, Fhiorinated metal fluorides oxides and metal fluorides as heterogeneous catalysts. Prog. Solid State Chem., 26, 97 (1998). 

TABLE 12.1 Single metal oxides as heterogeneous base catalysts. 

The basic concept is the intuition that, whether homogeneous or heterogeneous, catalysis is primarily a process controlled by a molecular phenomenon since it implies the catalyzed transformation of molecules into other molecules. It follows that on the surface of metals or metal oxides, sulfides, carbides, nitrides usually involved as heterogeneous catalysts, the relevant surface species and the mechanism of their mutual reactions must be of molecular character, as occurs in homogeneous or enzymatic catalysis. 

Within a discussion of nanostructured catalysts, mention must be made of zeolitic systems. Zeolites are a broad family of natural and synthetic aluminosiU-cates that exhibit two important properties that makes them ideal for consideration as heterogeneous catalysts they are crystalline and porous. Crystallinity brings with it precise definition at the atomic scale that is absent with amorphous or polycrystaUine metal oxides. The combination of a well-defined structure and... 

Further evidence has been obtained to support the contention that the active catalysts are metal complexes dissolved in solution. With experiments reported in Table II, the kinetics of oxidation under standard conditions in the presence of various metal salts are compared with the rates of reaction when solid residues have been filtered from solution. The agreement between the rates in Cases 1 and 3 of Table II (where the amount of metal available is dictated by the solubility of metal complexes) shows that solid precipitates play little or no part in catalysis in all the systems studied. The amount of metal in solution has been measured in Cases 2 and 3 metal hydroxide complexes (Case 2) are not as soluble as metal-thiol complexes, and neither is as soluble as metal phthalocyanines (19). The results of experiments involving metal pyrophosphates are particularly interesting, in that it has previously been suggested that cobalt pyrophosphates act as heterogeneous catalysts. The result s in Table II show that this is not true in the present system. 

A further development in the 1980s/1990s was the introduction of some newer catalysts. Narrow range or peaked ethoxylates can be made using acid activated metal alkoxides, metal phosphates or activated metal oxides as catalyst. These catalysts are insoluble and therefore heterogeneous in nature and the major process difference is that catalyst slurry is added to the reactor after which the conditions are exactly as with normal alkaline catalysts. The reactions are slightly quicker and need less catalyst but it must be filtered out. Most producers [ 12-20 ] have patents on these systems, the advantages of which are seen in the finished products as ... 

Metal-oxides of the type (Al203)x(Sn0)Y(Zn0)z were also studied as heterogeneous catalysts for the transesterification reaction of soybean oil (Macedo et al., 2006). It was observed that these materials are active for soybean oil alcoholysis with different alkyl-chain alcohols using several alcohols, including branched ones. The best result was achieved using methanol, with conversion yields up to 80% in 4 h. As observed for the complex 1 in homogenous conditions, the catalytic activities are strongly dependent on the nature of the alcohol. For alcohols with a linear chain, the reaction activities decrease with... 

Both hydrated and anhydrous metal borates have numerous industrial uses. Some of the major uses of hydrated metal borates are the manufacture of glasses, ceramics, and industrial fluids, and as micronutrient fertilizers, fire retardants, and biostats. Anhydrous borates find use as heterogeneous catalysts, scintillation hosts, and in the fabrication of optoelectronic devices. Anhydrous aluminum borates are used as additives in oxide ceramics to promote the formation of desirable phases. Also, aluminum borate whiskers are used as reinforcing additives in composite materials. Specific nses of sodium, calcium, zinc, and barium borates are discussed in sections below. 

However, this reaction is very slow in the absence of a catalyst. One of the mysteries during early research on air pollution was how the sulfur dioxide produced from the combustion of sulfur-containing fuels is so rapidly converted to sulfur trioxide in the atmosphere. It is now known that dust and other particles can act as heterogeneous catalysts for this process (see Section 15.9). In the preparation of sulfur trioxide for the manufacture of sulfuric acid, either platinum metal or vanadium(V) oxide (V205) is used as a catalyst, and the reaction is carried out at approximately 500°C, even though this temperature decreases the value of the equilibrium constant for this exothermic reaction. 

Another approach to designing shape-selective heterogeneous oxidation catalysts was to use redox metal oxides as the pillaring agents in the preparation of pillared clays. These redox pillared clays have been used for a number of selective oxidations. Chromium pillared montmorillonite (Cr-PILC) is an effective catalyst for the selective oxidation of alcohols with tert-butyl hydroperoxide. 7 Primary aliphatic and aromatic alcohols are oxidized to the aldehydes in very good yields. Secondary alcohols are selectively oxidized in the presence of a primary hydroxy group of a diol to give keto alcohols in excellent yields (Eqn. 21.12). 2... 

Heterogeneous catalysts are defined as solids or mixture of solids that are used to accelerate a chemical reaction without undergoing change themselves. The types of solids used in industry as heterogeneous catalysts include simple oxides, mixed oxides, metal salts, solid acids and bases, metals, and dispersed metals. Catalysts are used in a wide variety of chemical and environmental processes worldwide. The global value of fuels and chemicals produced by catalytic routes is about US 2.4-3 trillion per year. About 20% of all products produced in the United States are derived from a catalytic process of some form. As important as catalysis is to the world economy, the number of various chemicals used as a catalyst as well as the form and shape of the material vary as much as the number of processes that use catalysts. Fig. 1 is a picture of a number of various types of catalysts and illustrates the numerous possibilities of shapes and sizes. Naturally, the preparation processes of such a wide variety of products is also numerous. 

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