Condensation silicon alkoxide

The chemical reactivity of metal alkoxides towards hydrolysis and condensation depends mainly on the positive charge of the metal atom 5(M) and its ability to increase its coordination number N. As a general rule, the electronegativity of metal atoms decreases and their size increases when going from the top right of the periodic table to the bottom left. The corresponding alkoxides become progressively more reactive towards hydrolysis and condensation. Silicon alkoxides are rather stable, while cerium alkoxides are very sensitive to moisture. Alkoxides of electropositive metals must be handled with care under a dry atmosphere, otherwise precipitation occurs as water is present... 

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. 

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. 

The Stober method can be used to form core-shell silica nanoparticles when a presynthesized core is suspended in a water-alcohol mixture. The core can be a silica nanoparticle or other types of nanomaterials [46, 47]. If the core is a silica nanoparticle, before adding silicon alkoxide precursors, the hydroxysilicates hydrolyzed from precursors condense by the hydroxide groups on the surface of the silica cores to form additional layers. If the core is a colloid, surface modification of the core might be necessary. For example, a gold colloid core was modified by poly (vinylpyrrolidone) prior to a silica layer coating [46]. 

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. 

In addition to the examples discussed above, where the hybrid materials were derived from the alkoxides of the transition metals, it is necessary to mention that M(OR) (M = Ti, Zr) are the typical inorganic chain-forming reagents often added to the silicon alkoxides to play the cross-linking role between the organosilicon units, which increases the hardness and the refractive index of the hybrid materials. M(OR)n were also found to catalyze the condensation of siloxanes. 

Silica nanoparticles are commonly prepared by polymerization of appropriate precursors such as silicates, silicon alkoxides, or chlorides (Fig. 11.2).2 Besides the industrial methods, which rely mainly on condensation of sodium silicate in water induced by sodium removal through ion exchange, three different synthetic methods are currently used in research labs to prepare silica nanoparticles loaded with organic molecules. In the first method, proposed by Kolbe in 1956s and developed by Stober and coworkers in the late 1960s,6 the particles are formed via hydrolysis and... 

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],... 

Metal alkoxides act as cross-linking agents between organosilicon units, increasing the hardness of the materials. Tetrafunctional silicon alkoxides are more commonly employed, but transition metal alkoxides M(OR) (M = Ti, Zr, etc.) can also be used. They not only serve as cross-linking reagents, but can also increase the refractive index or catalyze condensation. 

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. 

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]. 

In the acidic route (with pH < 2), both kinetic and thermodynamic controlling factors need to be considered. First, the acid catalysis speeds up the hydrolysis of silicon alkoxides. Second, the silica species in solution are positively charged as =SiOH2 (denoted as I+). Finally, the siloxane bond condensation rate is kinetically promoted near the micelle surface. The surfactant (S+)-silica interaction in S+X 11 is mediated by the counterion X-. The micelle-counterion interaction is in thermodynamic equilibrium. Thus the factors involved in determining the total rate of nanostructure formation are the counterion adsorption equilibrium of X on the micellar surface, surface-enhanced concentration of I+, and proton-catalysed silica condensation near the micellar surface. From consideration of the surfactant, the surfactants first form micelles as a combination of the S+X assemblies, which then form a liquid crystal with molecular silicate species, and finally the mesoporous material is formed through inorganic polymerization and condensation of the silicate species. In the S+X I+ model, the surfactant-to-counteranion... 

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 ... 

The general theory of nucleation and polymerization in aqueous systems, in which silica shows some solubility, is discussed in detail in Iler s book (3). However, very little was known at the time the book was published (1979) about the polymerization of silica when Si(OH)4 is formed in nonaqueous systems. Progress made up to 1990 in the understanding of the hydrolysis and condensation of silicon alkoxides that leads to silica gels or to silica sols of large particle diameter are lucidly discussed by Brinker and Scherer (8). Brinker s chapter in this book (Chapter 18) includes a clear explanation of the difference between hydrolysis and condensation of aqueous silicates and silicon alkoxides. 

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. 

The hydrolysis and condensation of silicon alkoxides is an area of intense interest. The sol-gel process uses high-purity monomers for low-temperature production of fibers, monoliths, coatings, and powders. Structures of the polymers produced in the sol ultimately dictate both gel and glass properties. 

This chapter is a brief overview of silicon alkoxide hydrolysis and condensation and the resulting structures, emphasizing recent studies and unpublished work. Schmidt et al. (I) and more recently Brinker (2) have published excellent overviews of this chemistry this chapter attempts to amplify and complement these reports. 

---