Hydrolysis reactions silicon alkoxides

As one would expect from the similar electronegativities of Si and O, the hydrolysis of silicon alkoxides are significantly slower than other metal analogues. For identical metal coordination spheres and reaction conditions, the general order or reactivity... 

Inorganic silicate polymers prepared by the hydrolysis of silicon alkoxides evolve by a complicated reaction pathway. The structures can be described only in a statistical fashion by means of fractal geometry. The structures are... 

FIGURE 22.5 Schematic showing reaction mechanisms for (a) acid- and (b) base-catalyzed hydrolysis of silicon alkoxides. 

The hydrolysis mechanisms involve first a nucleophilic attack of oxygen lone pairs of the H2O molecule on the Si atoms [33]. Because of the polarized Si-O bonds, the silicon atoms hold a partial positive electrcMiic charge which in turn determines the kinetics of the nucleophilic attack and hence of the overall hydrolysis reaction. In alkoxides, the Si atoms carry a relatively moderate partial positive charge (e.g., 8" 0.32 in Si(OEt)4 by... 

Base-catalyzed hydrolysis of silicon alkoxides proceeds much more slowly than acid-catalyzed hydrolysis at an equivalent catalyst concentration. Basic aUcoxide oxygens tend to repel the nucleophile, -OH. However, once an initial hydrolysis has occurred, the following reactions proceed stepwise, with each subsequent... 

Hydrolysis addresses the effects of processing parameters, such as catalysts, H2O Si ratio, and solvent, as well as steric and inductive factors on the mechanism of hydrolysis of silicon alkoxides and the reverse reaction, esterification. 

As has been discussed before, hydrolysis of silicon alkoxides is faster than condensation under acidic conditions. Since all species are hydrolyzed at an early stage of the reaction, they can condense to form small oligomeric species (clusters) with reactive Si—OH groups. Under these conditions, reactions at terminal silicon atoms are fevored (see above). This results in polymer-hke gels that is, small clusters undergo condensation reactions with each other to give a polymer-like network with small pores. 

Employing silicon alkoxides, the hydrolysis has to be catalyzed by the addition of an acid or a base, and an excess of water is often used. Employing zirconium alkoxides, the hydrolysis reaction proceeds much faster than the condensation so that the product is obtained as a precipitate rather than a gel. 

Because of the role of precursor structure on film processing behavior (consolidation, densification, crystallization behavior), the reaction pathways are typically biased through the use of the catalyst, which is simply an acid or a base. This steers the reaction toward an electrophilic or nucleophilic attack of the M—OR bond.1,63 Hydrolysis sensitivity of singly or multiply hydrolyzed silicon alkoxides is also influenced by the catalyst, which contributes to the observed variations in oligomer length and structure. Figure 2.3b illustrates... 

The Stober method is also known as a sol-gel method [44, 45], It was named after Stober who first reported the sol-gel synthesis of colloid silica particles in 1968 [45]. In a typical Stober method, silicon alkoxide precursors such as tetramethylorthosili-cate (TMOS) and tetraethylorthosihcate (TEOS), are hydrolyzed in a mixture of water and ethanol. This hydrolysis can be catalyzed by either an acid or a base. In sol-gel processes, an acidic catalyst is preferred to prepare gel structure and a basic catalyst is widely used to synthesize discrete silica nanoparticles. Usually ammonium hydroxide is used as the catalyst in a Stober synthesis. With vigorous stirring, condensation of hydrolyzed monomers is carried out for a certain reaction time period. The resultant silica particles have a nanometer to micrometer size range. 

In 1968, Stober et al. (18) reported that, under basic conditions, the hydrolytic reaction of tetraethoxysilane (TEOS) in alcoholic solutions can be controlled to produce monodisperse spherical particles of amorphous silica. Details of this silicon alkoxide sol-gel process, based on homogeneous alcoholic solutions, are presented in Chapter 2.1. The first attempt to extend the alkoxide sol-gel process to microemul-sion systems was reported by Yanagi et al. in 1986 (19). Since then, additional contributions have appeared (20-53), as summarized in Table 2.2.1. In the microe-mulsion-mediated sol-gel process, the microheterogeneous nature (i.e., the polar-nonpolar character) of the microemulsion fluid phase permits the simultaneous solubilization of the relatively hydrophobic alkoxide precursor and the reactant water molecules. The alkoxide molecules encounter water molecules in the polar domains of the microemulsions, and, as illustrated schematically in Figure 2.2.1, the resulting hydrolysis and condensation reactions can lead to the formation of nanosize silica particles. 

Silica Nanoparticles. The base-catalyzed hydrolysis of silicon aikoxides in microemulsions produces nanoparticles (20-39). Aqueous ammonia has been used primarily as the base, with AOT and nonionic polyoxyethylene ethers as the main surfactants. Figure 2.2.6 presents a flow diagram for the synthesis of pure silica (23-32) the microemulsion is first prepared and then the alkoxide is added. As can be seen from Table 2.2.1, the microemulsions include the systems AOT/ isooctane/water/ammonia, AOT/toluene/water/ammonia, NP-5/cyclohexane/water/ ammonia, and NP-4/heptane/water/ammonia. Typical reaction times are l -5 days. Various modified silica nanoparticles have also been prepared, including hydropho-... 

Our synthesis is based on the hydrolysis of a silicon alkoxide (TEOS Si(OCH2CH3)4) in a diluted solution of nonionic polyethylene oxide-based surfactants. The hydrolysis is then induced by the addition of a small amount of sodium fluoride [5], Depending on the initial mixing conditions, the size of the solubilized objects leads to either a colorless or milky emulsion. Small particles ( 300 nm) with a 3D worm-hole porous structure or small hollow spheres with mesoporous walls, are usually obtained [6]. The synthesis we report herein after exhibits an apparently slight but actually drastic change in the preparation conditions. The main feature of this approach is an intermediate step that utilizes a mild acidity (pH 2 - 4), in which, prior to the reaction, a stable colorless microemulsion containing all reactants is... 

Another route for the production of materials involves the reaction of hydrolysis-condensation of metal alkoxides with water. We study here the important case of amorphous silica synthesis. In this case [38,39,44], silicic acid is first produced by the hydrolysis of a silicon alkoxide, formally a silicic acid ether. The silicic acids consequently formed can either undergo self-condensation, or condensation with the alkoxide. The global reaction continues as a condensation polymerization to form high molecular weight polysilicates. These polysilicates then connect together to form a network, whose pores are filled with solvent molecules, that is, a gel is formed [45],... 

The sol gel chemistry of sihcon alkoxides is much simpler (see Silicon Inorganic Chemistry)P Si is fourfold coordinated (N = z = 4,) in the precursor as well as in the oxide so that coordination expansion does not occur. The electronegativity of Si is rather high compared to transition metals. Silicon alkoxides are therefore not very sensitive toward hydrolysis. Their reactivity decreases when the size of the alkoxy groups increases. This is mainly due to steric hindrance, which prevents the formation of hypervalent sihcon intermediates (see Hypervalent Compounds). Silicon alkoxides, Si(OR)4, are always monomeric. Heterometallic alkoxides have never been obtained via the reaction of a sihcon alkoxide with another alkoxide. Silicon alkoxides have to be prehydrolyzed before Si T M bonds can be formed. 

Figure 2.44. Reaction schemes for the base-catalyzed hydrolysis and condensation of a silicon alkoxide precursor.

For example, Scheme I shows that hydrolysis of a silicon alkoxide results in the generation of an alcohol such as ethanol (in the case of TEOS). This small molecule must be removed from the system for suitable network development and solidification. Such removal would lead, in the limit, to a tetrahedral Si02 network. In addition, the condensation reaction of hydrolyzed silicon alkoxide results in the generation of water, which must also be removed. However, water can also promote additional hydrolysis during the reaction, as is obvious from Scheme I. Finally, Scheme I indicates that these reactions are promoted in either acidic or alkaline environments. 

The chemistry of these hydrolysis and condensation reactions is very complicated. Both reactions are pH sensitive. Acids and bases catalyze the hydrolysis reactions, although each to a different extent (i). The condensation reaction is also highly pH dependent. Water is consumed in the hydrolysis reaction but liberated in the condensation reaction. To fully activate all of the silanols initially requires twice as much water as is consumed in the net reaction. To use less water means the reactions will be closely coupled. The reactions are usually conducted in a solvent, because the alkoxides are immiscible with the water required for hydrolysis. The usual solvent is the alcohol corresponding to the alkoxide group of the silicon source, which is also a byproduct of the reactions. 

Relatively few studies on the synthesis of mesoporous alumina have been reported to date [8]. One of the limitations of the reported synthetic strategies is that the rate of hydrolysis (and condensation) reaction of aluminum alkoxide are much faster than that of silicon alkoxide. In this study, we proposed a novel method to prepare bimodal porous aluminas with meso- and macropores with narrow pore size distribution and well-defined pore channels. The fiamewoik of the porous alumina is prepared via a chemical templating method using alkyl caiboxylates. Here, self-assemblied micelles of carboxylic acid were used as a chemical template. Mesoporous aluminas were prepared through carefiil control of the reactants pH, while the procedures are reported elsewhere [9]. 

One major problem in producing gels containing homogeneous mixtures of a variety of oxides is that the precursors may not all hydrolyze at the same rate. In particular, transition metal alkoxides hydrolyze much more rapidly than silicon alkoxides. The controlled hydrolysis of low-molecular-weight homometallic species described in the previous section can be adapted to prepare mixed alkoxides. For example, pre-hydrolysis of metal alkoxide followed by reaction with the silicon alkoxide gives a mixed dimeric species such as ... 

Silicon alkoxides exhibit very slow hydrolysis and condensation reactions compared with other alkoxides of aluminum, titanium or zirconium generally used for membrane preparation. Accordingly, acid or basic catalysts are used in the case of silicon alkoxides while methods for the control of hydrolysis are advisable with transition metal alkoxides [36,37]. 

For silica gels a number of parameters have been demonstrated to have a large effect on the evolution of porosity and subsequently on the resulting silica materials [1]. Almost dense, micro- or mesoporous silica materials can be obtained depending on the experimental conditions in which hydrolysis and condensation reactions of silicon alkoxides are carried out. This is not the case for transition metal alkoxides which are very sensitive to hydrolysis. They do not cillow the adaptation of sol-to-gel transition in order to obtain controlled porous textures. Some years ago special attention was paid to the utilization of amphiphilic systems as reactive media to control hydrolysis and condensation kinetics with transition metal alkoxides [37]. In a more recent work Ayral et al. 

The chemistry involved in the formation of mesoporous silica thin films is qualitatively well understood. However, specific reaction mechanisms of the individual steps are still debated. In addition, owing to the complexity of the sol-gel reaction pathways and cooperative self-assembly, full kinetic models have not been developed. From the time of mixing, hydrolysis reactions, condensation reactions, protonation and deprotonation, dynamic exchange with solution nucleophiles, complexation with solution ions and surfactants, and self-assembly, all occur in parallel and are discussed here. Although the sol-gel reactions involved may be acid or base catalyzed, mesoporous silica film formation is carried out under acidic conditions, as silica species are metastable and the relative rates of hydrolysis and condensation reactions lead to interconnected structures as opposed to the stable sols produced at higher pH. Silicon alkoxides are the primary silica source (tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, etc.) and are abbreviated TMOS, TEOS, and TPOS, respectively. Starting from the alkoxide, Si(OR)4, in ROH and H2O solution, some of the general reactions are ... 

Making an aerogel involves base-catalyzed hydrolysis and polycondensation reactions of silicon alkoxides in an alcohol followed by 24 hours of aging in the alcohol solvent to produce an alcogel. Then the alcohol is removed from the pores of the alcogel... 

The Stober route (8) is a well-known method for providing submicro-meter- or micrometer-sized silica particles by hydrolysis and condensation of silicon alkoxide an excess of base and water is used in the reaction. Compared with this method, ours has quite different reaction conditions, namely, the use of a limited amount of water and a large amount of acid. In contrast to the reaction of silicon alkoxide with a large amount of water in basic conditions, Sakka and Kamiya (9) noticed from the measurement of the intrinsic viscosity of silica sols that linear particles or polymers, not round particles, are formed with acidic conditions and the addition of a small amount of water. Therefore, the reaction conditions for this method for producing round micrometer-sized particles is new, and the mechanism of formation of round particles is of interest. 

Stober et al. (15) developed a method of preparing remarkably uniform silica particles with sizes ranging from 50 nm to >1 pm in diameter. Their recipe involves hydrolyzing silicon alkoxides in aqueous alcoholic solutions containing ammonia. The resulting solids are amorphous and are 11-15% porous. We chose to use the hydrolysis and condensation of tetraethylor-thosilicate, TEOS, in ethanol as a model precipitation reaction to study parameters leading to uniformity. 

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