Catalytic superacidic metal oxides

Preparation of Superacidic Metal Oxides and Their Catalytic Action... 

Metal oxides, 31 78-79, 89, 102, 123, 157-158, 191, 32 199-121 see also Amorphous metal oxides Sulfate-supported metal oxides specific oxides adsorbed oxygen on, 27 196-198 binary, surface acidity, 27 136-138 catalytic etching, 41 390-396 coordination number, 27 136 electrocatalysts, 40 127-128 Fe3(CO)i2 reaction with, 38 311-314 Lewis acid-treated, 37 169-170 multiply-valent metals, electrocatalytic oxidations, 40 154-157 superacids by, 37 201-204 surface acidity, methods for determining, 27 121... 

Several metal oxides could be used as acid catalysts, although zeolites and zeo-types are mainly preferred as an alternative to liquid acids (Figure 13.1). This is a consequence of the possibility of tuning the acidity of microporous materials as well as the shape selectivity observed with zeolites that have favored their use in new catalytic processes. However, a solid with similar or higher acid strength than 100% sulfuric acid (the so-called superacid materials) could be preferred in some processes. From these solid catalysts, nation, heteropolyoxometalates, or sulfated metal oxides have been extensively studied in the last ten years (Figure 13.2). Their so-called superacid character has favored their use in a large number of acid reactions alkane isomerization, alkylation of isobutene, or aromatic hydrocarbons with olefins, acylation, nitrations, and so forth. 

This review summarizes the recent works on syntheses of solid superacids and their catalytic action, including Lewis acids and liquid superacids in the solid state, as discussed in Sections Il-IV. Sections VI and VII describe new types of solid superacids we have studied in this decade sulfate-supported metal oxides and tungsten or molybdenum oxide supported on zirconia. Perfluorinated sulfonic acid, based on the acid form of DuPont s Nafion brand ion membrane resin, is also gaining interest as a solid superacid catalyst Nafion-H-catalyzed reactions are reviewed in Section V. 

Benzylation of toluene with benzyl chloride, which is a typical example of Friedel-Crafts alkylation, is known to be catalyzed by Lewis-type superacids such as A1C13 and BF3. This type of catalyst has been mostly used for the Friedel-Crafts reaction, which is one of the most studied of organic reactions. This reaction was performed over several metal oxides and sulfates, and iron sulfates showed an unexpected effectiveness for the reaction (102-104). The catalytic activities of FeS04 and Fe2(S04)3 for the reaction were examined in detail the activities were remarkably dependent on calcination temperature, the maximum activity being observed with calcination at 700°C (105-107). Catalytic actions analogous to the above case were also observed with other Friedel-Crafts reactions, the benzoyl-ation of toluene with benzoyl chloride (108), the isopropylation of toluene with isopropyl halides (109), and the polycondensation of benzyl chloride UIO). 

In 2004, Jiang, et al. studied the esterification of n-pentanol with benzoic add using Al-pillared clay (PILC) supported 5042" /Ti02 superacid catalyst (Fang et al., 2010), and find that it is known that the generation of super acid sites in the system of 5042 /MJDy solid superacid is necessarily promoted by the sulfur of the metal oxides, the more acid sites formed, the higher catalytic activity exhibited. Therefore, Al-PILC carrier can effectively enhance the catalytic activity. 

Although the super acidity of sulphated zirconium oxide is widely accepted, Farca iu indicated that traditional acidity measurements, i.e. Hammett type, can not be applied to solid acids. He showed that the exceptional catalytic activity of sulphated zirconia and other sulphated metal oxides (SMO) is not justified by their acid strength and that they are in fact not superacidic at all. He argues that sulphated zirconium exhibits a bifunctional character in which oxidation in the initiation step is combined with acid catalysed reaction of the intermediates formed. Oxidation is normally achieved through the reduction of the sulphate or added redox promotors, which increases the catalytic activity but not the acid strength. 

We believe that catalysis occurs by formation of a complex between acetaldehyde, peracetic acid, and the metal ion in the 3+ oxidation state. The metal ion could be acting as a superacid as for peracetic acid decomposition, although oxidation-reduction reactions within the complex cannot be ruled out. Here again, we have found a disturbing lack of catalytic activity of other trivalent metals (aluminum, iron, and chromium). Simple acid catalysis is not as effective as proved when using p-toluenesulfonic acid and acetyl borate. This indicates that at least more than one coordination position is needed to obtain a complex of the proper configuration. 

---