Porosity, monoliths

In order to generate sufficient porosity, monoliths with a suitable microporosity (40 %) and microglobule diameter (1.5 0.5 pm) were synthesized. Consecutive in-situ derivatization was successfully accomplished using a mixture of norborn-2-ene and the corresponding NHC-precursor in methylene chloride (Scheme 1). The use of norborn-2-ene significantly enhances grafting yields for the functional monomer. Using this setup. 

Poco, J.F., Satcher, J.H., Jr., Hrubesh, L.W., 2001, Synthesis of high porosity monolithic alumina aerogel, J. Non-Cryst. Solids 285,57-63. 

Monolithic carbons may also be manufactured in finished form fi om PVDC as has been done by Quinn [18]. The porosity and density compare favourably with those of conventional granular carbons and the Sutcliffe Speakmann monoliths but the manufacturing process is not easy to scale up from the laboratory to commercial levels. The properties, (including K and n from the D-A equation) are compared in Table 3 below, taken from Critoph [4]. 

The next level is that of shaped catalysts, in the form of extrudates, spheres, or monoliths on length scales varying from millimeters to centimeters, and occasionally even larger. Such matters are to a large extent the province of materials science. Typical issues of interest are porosity, strength, and attrition resistance such that catalysts are able to survive the conditions inside industrial reactors. This area of catalysis is mainly (though not exclusively) dealt with by industry, in particular by catalyst manufacturers. Consequently, much of the knowledge is covered by patents. 

The monomers commonly used for the preparation of polymer monoliths are either hydrophobic, for example, styrene/divinylbenzene and alkyl methacrylates, or hydrophilic, for example, acrylamides. The polymerization is usually accomplished by radical chain mechanisms with thermal or photochemical initiation, as detailed in the reviews (Eeltink et al., 2004 Svec, 2004a and b). Internal structures of polymer monoliths are described to be corpuscular rather than spongy this means through-pores were found to be interstices of agglomerated globular skeletons as shown in Fig. 7.1 (Ivanov et al., 2003). Porosity is presumably predetermined by the preparation... 

Table 7.1 shows the pore properties of several polymer monolithic columns prepared from styrene/DVB, methacrylates, and acrylamides along with the feed porosity and column efficiency, summarized from several recent publications. Some important points seem to be clearly shown in Table 7.1, especially by the comparison of the properties between methacrylate-based polymer monoliths and silica monoliths. 

A rather limited range of mesopores in terms of size and volume were observed in the skeletons of polymer monoliths. The porosity of the polymer monolith seems to be lower than that of silica monolith. The total porosity of these monoliths is in the range of 0.61-0.73, whereas interstitial (through-pore) porosity and mesopore porosity are 0.28-0.70 and 0.03-0.24, respectively. In the case of poly(butyl methacrylate-co-ethylene dimethacrylate), the observed porosity is around 0.61-0.71, resulting in permeability 0.15-8.43 x 10 14 m2, whereas the observed porosity of silica monoliths prepared in a capillary is 0.86-0.96 and the permeability is 7-120 x 10 14 m2. Higher permeability will be advantageous for 2D applications, as mentioned later. 

High performance monolithic columns were prepared from styrene and divinyl-benzene (PSDVB, 200 pm i.d.) (Oberacher et al., 2004). The monoliths possess 5-300 nm pores with porosity of ca. 50% and 20% for external and internal pores, respectively, with specific surface areas of 30-40 m2/g. The column showed permeability K= 3.5 x 10 15m2 in water and slightly less in acetonitrile. The pore size... 

Chromatographic use of monolithic silica columns has been attracting considerable attention because they can potentially provide higher overall performance than particle-packed columns based on the variable external porosity and through-pore size/skeleton size ratios. These subjects have been recently reviewed with particular interests in fundamental properties, applications, or chemical modifications (Tanaka et al., 2001 Siouffi, 2003 Cabrera, 2004 Eeltink et al., 2004 Rieux et al., 2005). Commercially available monolithic silica columns at this time include conventional size columns (4.6 mm i.d., 1-10 cm), capillary columns (50-200 pm i.d., 15-30 cm), and preparative scale columns (25 mm i.d., 10 cm). 

Al-Bokari, M., Cherrak, D., Guiochon, G. (2002). Determination of the porosities of monolithic columns by inverse size-exclusion chromatography. J. Chromatogr. A 975, 275-284. 

Brandhuber, D., Torma, V., Raab, C., Peterlik, H., Kulak, A. and Husing, N. (2005) Glycol-modified silanes in the synthesis of mesoscopically organized silica monoliths with hierarchical porosity. Chemistry of Materials, 17, 4262 1271. 

Monoliths comprising cross-linked organic media with a well-defined porosity have emerged as useful supports for immobilizing catalysts. These supports offer advan-... 

FIGURE 4.7 Calibration curves for Ca2+-selective membrane electrodes made from a monolith of low porosity (i.d., 200 pm, no PVC) with inner filling solution of 0.1 M CaCl2 (a) and time response of the monolithic Ca2+-ISE (b). (Figures adapted from [32].)... 

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