Controlled-pore/porous glass

Pore size control in porous glass-ceramics with skeleton of NASICON-type crystal CaTi4(P04)6. J. Non-Cryst. Solids, 139, 90-92. 

Porous glasses and silica gels with controlled pore sizes which are rigid... 

Some bead materials possess porous structure and, therefore, have very high surface to volume ratio. The examples include silica-gel, controlled pore glass, and zeolite beads. These inorganic materials are made use of to design gas sensors. Indicators are usually adsorbed on the surface and the beads are then dispersed in a permeation-selective membrane (usually silicone rubbers). Such sensors possess high sensitivity to oxygen and a fast response in the gas phase but can be rather slow in the aqueous phase since the gas contained in the pores needs to be exchanged. Porous polymeric materials are rarer and have not been used so far in optical nanosensors. 

Figures 11.1 and 11.2 illustrate mercury porosimetry data of a bimodal size distribution. However, other types of less typical curves are often encountered. For example, samples of controlled porous glass exhibit intrusion-extrusion curves illustrated by Fig. 11.3, in which all the pores are essentially of one radius.

A number of recent developments in 129Xe NMR spectroscopy are presented with direct applications to the study of mesopore space in solids. This includes the establishment of a relationship between pore size and chemical shifts for a number of controlled pore glasses and the exploration of hyperpolarized (HP) xenon for a number of NMR and microimaging applications to porous solids. With HP xenon, the increase in experimental sensitivity is remarkable. Experiments illustrated include the rapid characterization of the void space in porous solids, including the in-situ study of processes such as diffusion and dehydration, and imaging with chemical shift resolution. 

Zeolites provide a novel host for the generation of semiconductor hyperlattices within their pore volume. The control of the connectivity between the clusters of semiconductor is unparalleled in any other host medium and so has allowed a detailed study of the optical consequences of such connectivity6. However, from the practical standpoint, such materials have some severe drawbacks - most notably the lack of single crystals of sufficient size to produce viable optical devices such as optical transistors or spatial light modulators. We have therefore moved on to look at more practical/processable quantum-dot materials such as semiconductor-doped porous glasses. 

Highly porous silica gel served as a support for the TADDOL moiety derived from inexpensive and readily available i-tartaric acid, which provided access to htanium-based Lewis acid catalysts (Heckel, 2000). Such entihes are employed successfully for enantioselective reactions. TADDOLs were covalently attached to the trimethyl-silyl-hydrophobized silica gel, controlled-pore glass (CPG) at about 300 m2 g-1, at a loading of 0.3-0.4 mmol gl (Heckel, 2002). In a carefully monitored mulh-step immobilization procedure, the TADDOLs were titanated to yield dichloro-, diisopropyl-, or ditosyl-TADDOLates. These catalysts were employed in dialkylzinc addihon to benzaldehydes and diphenyl nitrone addihon to 3-crotonyloxazolidinone, a [3+2] cycloaddition. 

A dry packed column with porous material was used for the characterization according to size of the PVAc latex samples. The packing employed was CPG (Controlled Pore Glass), 2000 A, 200-400 mesh size. Deionized water with 0.8 gr/lit Aerosol O.T. (dioctyl sodium sulphosuccinate), 0.8 gr/lit sodium nitrate and 0.4 gr/lit sodium azide served as the carrier fluid under a constant flowrate. The sample loop volume was 10 pC A Beckman UV detector operating at 254 nm was connected at the column outlet to monitor particle size. A particle size-mean retention volume calibration curve was constructed from commercially available polystyrene standards. For reasons of comparison, the samples previously characterized by turbidity spectra were also characterized by SEC. A number of injections were repeated to check for the reproducibility of the method. 

Fractal plots of log nm versus log a for two porous silicas are shown in Figure 63 (here, nm is the BET monolayer capacity). Both plots are linear, giving Dx = 2.98 for the silica gel and Dx = 2.09 for the controlled pore glass. These values reflect the extremes of the fractal scale, the latter being close to the ideal value for a flat surface. 

Porous glasses and silica gels with controlled pore sizes which are rigid and non-compressible are particularly useful in separations where the mobile phase is pressurized as in hplc (p. 112, table 4.18). 

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