Silica pore diameter, effects

Silica gels with mean pore diameters of 5-15 nm and surface areas of 150-600 m /g have been preferred for the separation of low molecular weight samples, while silica gels with pore diameters greater than 30 nm are preferred for the separation, of biopolymers to avoid restricting the accessibility of the solutes to the stationary phase [15,16,29,34]. Ideally, the pore size distribution should be narrow and symmetrical about the mean value. Micropores are particularly undesirable as they may give rise to size-exclusion effects or irreversible adsorption due to... 

Sabi, A. M., Claeys, M., and van Steen, E. 2002. Silica supported Fischer-Tropsch catalysts Effect of pore diameter of support. Catal. Today 71 395 402. 

Similarly, Hg(n) binding to thiol-functionalized mesoporous silica for which effective access to all the binding sites (100% of SH groups com-plexed with Hg(n) was achieved in micelle-templated mesostructures with pore diameters larger than 2.0 nm, whereas incomplete filling was always observed with corresponding amorphous silica-based adsorbents.37... 

Membranes with extremely small pores ( < 2.5 nm diameter) can be made by pyrolysis of polymeric precursors or by modification methods listed above. Molecular sieve carbon or silica membranes with pore diameters of 1 nm have been made by controlled pyrolysis of certain thermoset polymers (e.g. Koresh, Jacob and Soffer 1983) or silicone rubbers (Lee and Khang 1986), respectively. There is, however, very little information in the published literature. Molecular sieve dimensions can also be obtained by modifying the pore system of an already formed membrane structure. It has been claimed that zeolitic membranes can be prepared by reaction of alumina membranes with silica and alkali followed by hydrothermal treatment (Suzuki 1987). Very small pores are also obtained by hydrolysis of organometallic silicium compounds in alumina membranes followed by heat treatment (Uhlhom, Keizer and Burggraaf 1989). Finally, oxides or metals can be precipitated or adsorbed from solutions or by gas phase deposition within the pores of an already formed membrane to modify the chemical nature of the membrane or to decrease the effective pore size. In the last case a high concentration of the precipitated material in the pore system is necessary. The above-mentioned methods have been reported very recently (1987-1989) and the results are not yet substantiated very well. 

Fig. 2. Effect of silica pore structure on separation. Stationary phases are 10 LiChrospher SI 100, SI 00, SI 1000, and SI 4000 having 100, 500, 1000. and 4000 A mean pore diameter, respectively. Rowrate and inlet pressure are 5 ml/min and 125 bar, respectively. Sample components I, benzene 2. diphenyl 3, m-terphenyl 4, m-quaterphenyl 5, m ipiliiqiicphcnyl 6, m-sexiphenyl. (Cotiuesy of Merck AO.)...

The effect of pore size on the retentive capacity of various octadecyl silica bonded phases is illustrated in Fig. 10. Exclusion effects become appreciable when bulky octadecyl groups (see Table V) are attached to the pore wall in 6 nm pore diameter silica (Si-60). As a result, the stationary... 

In section 6.3.1 it was described, that macroporous silica particles are veiy effective carriers for lipase inunobilization, provided that the pore diameter is larger than about 500A. For industrial use the particle size catmot be less than 200-300 m. 

Unfortunately, even this modified equation does not describe the true practical situation in LC, as it is complicated by the fact that all silica-based materials exhibit exclusion properties. The pore diameter of silica-based stationary phases can range from, perhaps, 2-3 Angstrom to as much as 1000-2000 Angstrom. Consequently, some, otherwise open pores, are accessible to the solute while others are not, depending on the size of the molecule. Therefore, only those pores that have a diameter equal to, or greater than, that of the solute molecules are accessible and only the stationary phase within those pores can effect retention. In addition, the static interstitial volume between the particles can also exhibit exclusion properties and some of the static interstitial volume may also be inaccessible to the larger solutes. As a consequence, equation (12) must be further modified to give,... 

No experiments with variation in particle size of the silica gel have been done to study intraparticle diffusion effects. In silica gel such diffusion would be only through the pores (analogous to the macropores of a polystyrene) since the active sites lie on the internal surface. The silica gel used by Tundo had a surface area of 500 m2/g and average pore diameter of 60 A.116). Phosphonium ion catalyst 28 gave rates of iodide displacements that decreased as the 1-bromoalkane chain length increased from C4 to Cg to C16, The selectivity of 28 was slightly less than that observed with soluble catalyst hexadecyltri-n-butylphosphonium bromide U8). Consequently the selectivity cannot be attributed to intraparticle diffusional limitations. 

In analogy to the loading step study, the effect of substrate structure has been studied by modifying mesoporous silica gels with a variable mean pore diameter.28 Sample pretreatment and curing (20 h, 423 K) were performed under vacuum. Variation of the pretreatment temperature causes a change in specific surface area and silanol number. 

For the preparation of tubular silica membranes, commercially available mesoporous membranes [17] are used. These tubular supports have a total length of 25 cm and are enamelled at both ends, required for a gas-tight sealing with carbon seals to the reactor, so that an effective porous length of 20 cm remains. The tube consists of 4 layers. Layer 1, 2 and 3 consist of a-alumina with a thickness of 1.5 mm, 40 and 20 im and a pore diameter of 12, 0.9 and 0.2 im respectively. Layer 4 consists of y-alumina with a thickness of 3-4 im a Kelvin radius of 4 nm. A schematic drawing of the cross-section of a mesoporous support tube is provided in Figure 4. 

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