Acid-base/redox catalysts

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... 

Each zeolite type can be easily obtained over a wide range of compositions directly by synthesis and/or after various post synthesis treatments. Moreover, various compounds can be introduced or even synthesized within the zeolite pores (ship in a bottle synthesis). This explains why zeolites can be used as acid, base, acid-base, redox and bifunctional catalysts, most of the applications being however in acid and in bifunctional catalysis. 

As described above, most industrial catalysts are mixed oxides of at least two oxide phases, because catalyst performance is greatly improved by mixing different oxides, according to be following mechanisms (i) stabilization, (ii) control of redox properties, (iii) creation of acidity and basicity, (iv) control of electronic and coordination state of the metal ion, and (v) combination of more than two frinctions to evolve acid-oxidation and acid-base bifrinctional catalysts. Examples are provided in the following sections. 

The main principles of using molecular sieve catalysts for intermediates and fine chemical synthesis are reviewed and critically discussed. Emphasis is placed on describing the role of the elementary steps. The role of the catalytic functions (acid-base, redox and host for catalytically active sites) and the role of the pore constraints in activity and selectivity are compared. Examples of successful applications are presented. 

Bautista, F.M., Campelo, JA4., Luna, D., Luque, J., and Marinas, JA4. (2006) Influence of the acid base/redox properties of TiO -sepiolite supported vanadium oxide catalysts in the gas-phase selective oxidation of toluene. Catal Today, 112, 28-32. 

A. Pantazidis, A. Auroux, J.-M. Herrmann and C. Mirodatos, Role of acid-base, redox and structural properties of VMgO catalysts in the oxidative dehydrogenation of propane, Catal Today, 32, 81-88 (1996). 

Write the balanced chemical equation for (a) the thermal decomposition of potassium chlorate without a catalyst (b) the reaction of bromine with water (c) the reaction between sodium chloride and concentrated sulfuric acid, (d) Identify each reaction as a Bronsted acid—base, Lewis acid—base, or redox reaction. 

The obtained results evidence the differences between RUS2 and M0S2. The former solid has a pseudometallic behavior whereas for M0S2 redox or acid base properties are involved. This demonstrates the difficulties encountered when the interaction of the reactants and the catalyst are described at a molecular level. 

It is worth mentioning that both the carboxylation of epoxides and anilines are acid-base reactions, which do not entail redox processes. Therefore a catalyst active in these reactions must provide acid-base functionality. In this perspective, positively charged gold could be the real player, although a co-catalytic or promotion effect of ze-rovalent gold could also be important. Therefore the catalysts for the oxidative carbonylation of aniline, supported on Merck Ion-exchanger IV, could be actually bifunctional. On one side, Au could catalyze the oxidation of CO with O2 to CO2, a reaction for which it is... 

The reduction of dioxygen to its fully reduced form, H20, requires the transfer of 4 electrons, and the transfer may proceed via a series of intermediate oxidation states, such as 02 /H00, HOO /HOOH, 0 /OH. These reduced forms of oxygen exhibit different redox properties and in the presence of substrate(s) and/or catalyst(s) may open different reaction paths for the electron transfer process. Fast proton transfer reactions between the corresponding acid-base pairs can introduce composite pH dependencies into the kinetic and stoichiometric characteristics of these systems. 

The transition between the two limiting situations is a function of the parameter (k-e/kc)Cp. The ratio between the catalytic peak current, ip, and the peak current of the reversible wave obtained in the absence of substrate, Pp, is thus a function of one kinetic parameter (e.g., Xe) of the competition parameter, (k e/A c)c and of the excess ratio y = C /Cp, where and Cp are the bulk concentrations of the substrate and catalyst, respectively. In fact, as discussed in Section 2.6, the intermediate C, obtained by an acid-base reaction, is very often easier to reduce than the substrate, thus leading to the redox catalytic ECE mechanism represented by the four reactions in Scheme 2.13. Results pertaining to the EC mechanism can easily be transposed to the ECE mechanism by doubling the value of the excess factor. 

The oxides represent one of the most important and widely employed classes of solid catalysts, either as active phases or as supports. They are used for both their acid-base and ReDox properties and constitute the largest family of catalysts in heterogeneous catalysis [76]. 

Metal oxides are an important elass of heterogeneous catalysts. They find direct application in a variety of reactions, from acid-base to redox reactions, in photocatalytic processes, and as catalysts for environmental protection. In addition, they are widely used as supports for other active components (metal particles or other metal oxides), although often they act not only as a support, but actively participate in the reaction mechanism." ... 

Oxides of transition metals can act as acid-base or redox catalysts. Oxides of non-transition metals (AI2O3, SiOj) are, however, good acid-base catalysts. There is a large family of aluminosilicate zeolitic acids (e.g. H -ZSM-5, H-mordenite). Micropor-ous aluminium phosphates (ALPOs) can be modified to yield acidic SAPOs (Si replaces... 

This is probably also a reaction of Class B, which however may be expected not to be pH dependent. Therefore, taking into account the scanty evidence available, we may propose that the catalytic activity for this reaction is also dependent on the redox properties of the catalyst, but that the direction of the reaction, either into ammonia and nitrogen or into nitrogen hydrogen respectively, may be connected with acid/base properties. 

There has been a resurgence of interest in proton-coupled redox reactions because of their importance in catalysis, molecular electronics and biological systems. For example, thin films of materials that undergo coupled electron and proton transfer reactions are attractive model systems for developing catalysts that function by hydrogen atom and hydride transfer mechanisms [4]. In the field of molecular electronics, protonation provides the possibility that electrons may be trapped in a particular redox site, thus giving rise to molecular switches [5]. In biological systems, the kinetics and thermodynamics of redox reactions are often controlled by enzyme-mediated acid-base reactions. 

Once the multi-step reaction sequence is properly chosen, the bifunctional catalytic system has to be defined and prepared. The most widely diffused heterogeneous bifunctional catalysts are obtained by associating redox sites with acid-base sites. However, in some cases, a unique site may catalyse both redox and acid successive reaction steps. It is worth noting that the number of examples of bifunctional catalysis carried out on microporous or mesoporous molecular sieves is not so large in the open and patent literature. Indeed, whenever it is possible and mainly in industrial patents, amorphous porous inorganic oxides (e.g. j -AEOi, SiC>2 gels or mixed oxides) are preferred to zeolite or zeotype materials because of their better commercial availability, their lower cost (especially with respect to ordered mesoporous materials) and their better accessibility to bulky reactant fine chemicals (especially when zeolitic materials are used). Nevertheless, in some cases, as it will be shown, the use of ordered and well-structured molecular sieves leads to unique performances. 

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