Aluminas hydroxyl groups

As [Fe(CO)s] readily reacts with alumina hydroxyl groups to provide the [HFe3(CO)ii] trinuclear immobilized iron cluster (Figure 9.5) with simultaneous... 

Figure 9.5 Surface organometallic chemistry of iron pentacarbonyl with alumina hydroxyl groups.

Boron also reacts with hydroxyl-containing polymers such as cellulose. When exposed to a flame the boron and hydroxyl groups form a glassy ester that coats the substrate and reduces polymer degradation. A similar type of action has been observed in the boron—alumina tfihydrate system. 

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Another contribution to die reaction involving steam is thought to be the role of the oxide support in the provision of hydrogen to the surface of adjacent catalyst particles. It is suggested drat die water molecule is adsorbed on the surface of oxides such as alumina, to form hydroxyl groups on the surface, thus... 

Eigure 3.56 depicts LEIS spectra for two completely different types of AI2O3 sample, i. e. a-alumina (sapphire) and y-alumina (a powder with high specific surface area) which show very similar results in both cases after thermal treatment at 400 °C [3.142]. Reduction of the A1 signal in y-alumina was ascribed to shielding by hydroxyl groups formed by water molecules, which are typical adsorbates on y-alu-mina. 

Of all the aluminas, y-alumina is the most used alumina, due to its high surface area and the high concentration of surface hydroxyl groups. 1 1-alumina is u.sed in i.somerization becau.se it has a higher density of acid sites at the surface. 

The retention of water in the form of hydroxyl groups by the alumina support is an important factor in slowing down the reduction rate and preventing complete reduction. 

In catalyst preparation, one can use this knowledge to determine the relative contributions of various hydroxyl groups before and after application of the active phase onto the support. In this way Sibeijn etal. [31] established that rhenium oxide attached to acidic sites of the alumina support exhibits higher activity for the metathesis of olefins than rhenium oxide on neutral or basic sites. As, however, rhenium species preferentially exchange with basic hydroxyls, one needs to increase the loading above a certain value (6 wt% for an alumina of 200 m2/gram) before the catalyst exhibits appreciable activity [31]. 

Hydroxyl groups on oxide and carbon surfaces are often modeled as a one-site, two-pK model as shown in Figure 6.1. Defend this choice of model with the pH shift data for alumina (Figure 6.15). Might a different type of site be envoked for silica (Figure 6.20) and unoxidized carbon (Figure 6.26a) See [21] for more other types of acid-base group models. 

The Lewis base sites of the aluminas also participate in the dehydration of primary and secondary alcohols by the removal of a proton from either the j8- or y-carbon atom in relation to the a carbon containing the hydroxyl group. 

The trans elimination can take place if the basic sites of the alumina attack the hydrogen from one side of the plane and the hydroxyl group is removed from the opposite side of the plane by the acidic sites of the alumina. This may be possible if the reaction occurs within the pores of molecular dimensions (46) or within the crevices of the aluminas. Crevice sites on silica-alumina catalyst have been proposed by Burwell and co-workers (57) on the basis of racemization and exchange reactions of hydrocarbons. 

---