Acid-Treated Metal Oxides

An impressive number of papers and books has been published and numerous patents have been registered on the aq lation of aromatic compounds over solid catalysts. Recently Sartori and Maggi [1] have written an excellent review with 267 references on the use of solid catalysts in Friedel-Crafts acylation. In one section of this review, namely acylation of aromatic ethers or thioethers, the authors report work on acylation by solid catalysts such as zeolites, clays, metal oxides, acid-treated metal oxides, heteropolyacids or Nafion. When examining in details these results, it appeared very difficult for us to build upon these experimental results as the reaction conditions differ drastically from one paper to the next. This prompted us to reinvestigate the scope and limitations of the Friedel-Crafts acylation using heterogeneous solids as catalysts, trying as much as we could to rationalize the observed effects. 

The metal oxide is treated with hydrofluoric acid. The fluoride formed is reduced with calcium. The advantage of using the fluoride instead of the oxide is that liquid calcium fluoride and not solid calcium oxide is formed. This can easily be separated from the pure RE metal. In a subsequent high-temperature process calcium residues are vaporized in vacuum. A very pure RE metal remains. This technique is used for production of the following metals [boiling point ("C) in parentheses] La (3457), Ce (3427), Pr (3520), Nd (3074), Gd (3273), Tb (3230), Dy (2567), Ho (2700), Er (2868), Lu (3402). 

Only copper can be electropolished in such a simple solution, but by minor modification other metals can be treated. Such modifications include (a) increasing the acidity, or (b) increasing the oxidant level for aluminium, iron and steel, nickel alloys etc ... 

Fig. 4 shows the SEM images of SWNTs purified by the thermal oxidation and acid-treated. Fig. 4(a) shows a SEM image of the raw soot. In addition to the bundle of SWNTs, carbonaceous particles are shown in the figure. These stractural features mi t be causal by various in the arcing process because of an inhomogeneous distribution of catalysts in the anodes [7]. It can be seen that the appearance of SWNTs was curled and quite different fiom that of MWNTs. Fig. 4(b) shows a decrease of amorphous carbons after oxidation. The basic idea of the selective etching is that amorphous carbons can be etched away more easily than SWNTs due to the faster oxidation reaction rate [2]. Since the CNTs are etched away at the same time, the yield is usually low. The transition metals can be etched away by an add treatment. Fig. 4(c) shows the SEM image of the acid-treated sample, where the annealed sample was immersed in 10 % HCl. 

It is useful to treat the raffinate to recover the two acids it contains. The raffinate can first be subjected to a thermal treatment which decomposes it into insoluble metallic oxides, hydrofluoric acid and sulfuric acid. In a first scrubbing, sulfuric acid is recovered, whilst in a second stage, hydrofluoric acid is absorbed. When put into operation, this process not only causes a reduction in the amount of sludges but also leads to acid production for return to the process. 

First there are the physical chemists, chemical engineers, and surface scientists, who study mainly nonpolar hydrocarbon reactions on clean and relatively clean metals and metal oxides. These have been the traditional studies formerly driven by the petroleum industry and now driven by environmental concerns. These workers typically treat the surface as a real entity composed of active sites (usually not identified, but believed in). These investigators typically, although not always, interpret mechanisms in terms of radical reactions on metals and in terms of acid-base reactions on metal oxides. 

The acid reflux procedure was first described by Rinzler el al. [28], in which raw nanotube materials are refluxed in nitric acid to oxidize the metals and carbon impurities. Acid-treated CNTs are considered to have carboxylic acid groups at the tube ends and, possibly, at defects on the side walls. The functionalized SWNTs have considerably different properties from those of the pristine tubes. 

In 1990, Choudary [139] reported that titanium-pillared montmorillonites modified with tartrates are very selective solid catalysts for the Sharpless epoxidation, as well as for the oxidation of aromatic sulfides [140], Unfortunately, this research has not been reproduced by other authors. Therefore, a more classical strategy to modify different metal oxides with histidine was used by Moriguchi et al. [141], The catalyst showed a modest e.s. for the solvolysis of activated amino acid esters. Starting from these discoveries, Morihara et al. [142] created in 1993 the so-called molecular footprints on the surface of an Al-doped silica gel using an amino acid derivative as chiral template molecule. After removal of the template, the catalyst showed low but significant e.s. for the hydrolysis of a structurally related anhydride. On the same fines, Cativiela and coworkers [143] treated silica or alumina with diethylaluminum chloride and menthol. The resulting modified material catalyzed Diels-Alder reaction between cyclopentadiene and methacrolein with modest e.s. (30% e.e.). As mentioned in the Introduction, all these catalysts are not yet practically important but rather they demonstrate that amorphous metal oxides can be modified successfully. 

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... 

Very acidic (high valent) cations will readily hydrolyse in aqueous solution, often even at low pH. These cations tend to form the polymeric metal oxide chains mentioned previously. This hydrolysis can be controlled by addition of boric acid (see Sec. 3.2.4.4) and forms the basis of a technique referred to as liquid phase deposition. This method can be reasonably included in the more general term of chemical solution deposition, and is treated, although not comprehensively, in this book. Ref 5 deals more thoroughly with this technique and describes many cases of SiOi as well as some examples of several other oxides not covered in this chapter. 

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