Pore, aerogel

Adsorption-desorption isotherms demonstrate the sharp contrast between a small pore silica xerogel and a large pore aerogel structure. 

Power M, Hosticka B, Black E, Daiteh C, Norris P (2001) ACTOgels as biosensms viral particle detection by bacteria immobilized rm large pore aerogeL J Nrm-Cryst Solids 285 303 308... 

Fig. XVII-29. Nitrogen isotherms the volume adsorbed is plotted on an arbitrary scale. The upper scale shows pore radii corresponding to various relative pressures. Samples A, Oulton catalyst B, bone char number 452 C, activated charcoal F, Alumina catalyst F12 G, porous glass S, silica aerogel. (From Ref. 196).

It is less well known, but certainly no less important, that even with carbon dioxide as a drying agent, the supercritical drying conditions can also affect the properties of a product. Eor example, in the preparation of titania aerogels, temperature, pressure, the use of either Hquid or supercritical CO2, and the drying duration have all been shown to affect the surface area, pore volume, and pore size distributions of both the as-dried and calcined materials (34,35). The specific effect of using either Hquid or supercritical CO2 is shown in Eigure 3 as an iHustration (36). 

Thus, the porosity of an aerogel is ia excess of 90% and can be as high as 99.9%. As a consequence of such a high porosity, aerogels have large internal surface area and pore volume. 

Siace the pores ia an aerogel are comparable to, or smaller than, the mean free path of molecules at ambient conditions (about 70 nm), gaseous conduction of heat within them is iaefficient. Coupled with the fact that sohd conduction is suppressed due to the low density, a siUca aerogel has a typical thermal conductivity of 0.015 W/(m-K) without evacuation. This value is at least an order of magnitude lower than that of ordinary glass and considerably lower than that of CFC (chloro uorocarbon)-blown polyurethane foams (54). 

Catalysis. Kistler explored the catalytic appHcations of aerogels ia the 1930s because of the unique pore characteristics of aerogels (24), but this area of research stayed dormant for about three decades until less tedious procedures to produce the materials were introduced (25,26). Three recent review articles summarize the flurry of research activities since then (63—65). Table 3 is a much abbreviated Hst of what has been cited in these three articles to demonstrate simply the wide range of catalytic materials and reactions that have been studied. 

Fig. 7. The effect of preparation on the pore size distribution (a), titanium dispersion (b), and the activity for epoxidation of cyclohexene (c) of titania—siUca containing 10 wt % titania and calcined in air at 673 K. Sample A, low-temperature aerogel Sample B, high-temperature aerogel Sample C, aerogel.

Production of net-shape siUca (qv) components serves as an example of sol—gel processing methods. A siUca gel may be formed by network growth from an array of discrete coUoidal particles (method 1) or by formation of an intercoimected three-dimensional network by the simultaneous hydrolysis and polycondensation of a chemical precursor (methods 2 and 3). When the pore Hquid is removed as a gas phase from the intercoimected soHd gel network under supercritical conditions (critical-point drying, method 2), the soHd network does not coUapse and a low density aerogel is produced. Aerogels can have pore volumes as large as 98% and densities as low as 80 kg/m (12,19). 

Figure 1. Influence of T1O2 content of LT-aerogels on relative proportion of Si-O-Ti connectivities R = [Si-0-Ti]/(Si-0-Si], mean pore diameter, and initial rate (to) of a-iso-phorone ep>oxidation with t-butyl hydroperoxide at 60 C. Data taken from ref. [18].

Both xerogels and aerogels are characteristically high surface area materials (surface areas normally exceed 500 m2/g). Unlike wet gels, many uses exist for dried gels due to their high surface areas and small pore sizes (typically, < 20 nm diameters). Examples include catalyst supports (12.). ultrafiltration media (18), antireflective coatings (19-20), and ultra-low dielectric constant films. (Lenahan, P. M. and Brinker, C. J., unpublished results.)... 

The first phase in the process is the formation of the sol . A sol is a colloidal suspension of solid particles in a liquid. Colloids are solid particles with diameters of 1-100 nm. After a certain period, the colloidal particles and condensed silica species link to form a gel - an interconnected, rigid network with pores of submicrometer dimensions and polymeric chains whose average length is greater than one micrometer. After the sol-gel transition, the solvent phase is removed from the interconnected pore network. If removed by conventional drying such as evaporation, so-called xerogels are obtained, if removed via supercritical evacuation, the product is an aerogel . 

Titania-silica aerogels possess very high surface areas (600 to 1000 m2/g) and large pore volumes (1 to 4 cm3/g), and thereby have attracted considerable interest for photocatalysis. A number of studies have shown that titania-silica intimate mixtures exhibit enhanced UV photocatalytic activity compared with pure titania [180-183],... 

Aerogels and Related Nanostructures—Aperiodic Pore-Solid Architectures... 

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