화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.121, No.37, 8533-8543, 1999
Surfactant-induced modification of dopants reactivity in sol-gel matrixes
Organically and bio-organically doped sol-gel materials have attracted much attention due to their ability to reproduce solution molecular activities within the ceramic environment. We take now this methodology one step forward and explore conditions under which the dopant properties can be modified by the matrix. Specifically we report that the co-entrapment of the surfactant cetyltrimethylammonium bromide (CTAB, the modifier) at low concentrations, with an extensive series of pH indicators representing several key molecular families (the primary dopant) within tetramethoxysilane (TMOS)-derived silica sol-gel matrixes, greatly modifies the indicating performance of the primary dopant. Thus, very large pK(i) shifts of up to 3-4 orders of magnitude obtained upon the co-entrapment cause methyl orange (MO) to become an; indicator for higher acidities and phenolphthalein for higher basicities, compared to their solution behavior. In another example, the Delta pK(i) between the two indicating transitions of alizarin increased from similar to 4.5 PK units in solution to similar to 10.5 pH units (!) in the glass, transforming it into an indicator for both the high acidic and high basic pH ranges. In yet another example, the two indicating transitions of phenol red were shifted to a more acidic pH range, pushing the tail of the more acidic titration branch into the negative pH values range. These and other effects were found to be more pronounced by the co-entrapment than by the use of CTAB solutions or of sol-gel matrixes without CTAB, pointing to a synergetic effect between the surfactant and the silica cage. The indicators also proved highly sensitive in revealing the properties of the local environment created by the surfactant. Thus, the indicator molecules were shown to migrate and reorient within the hydrophobic and the hydrophilic regions of micellar environment, according to their acquired charge upon pH changes. The concentration-dependent and humidity-dependent surfactant aggregation processes within the silica cage were probed with MO, and the results were compared with the behavior of entrapped MO in sol-gel matrixes of varying hydrophobicities, obtained by the copolymerization of CH3Si(OCH3)(3) with TMOS at various ratios, with and without CTAB. Of practical importance have been the observations that the dopant/surfactant co-entrapment greatly improves the leaching profiles: half-lives, ranging from several months to several years, were found for MO and methyl red; and using SAXS, surface area and porosity measurements, it was shown that CTAB can be used to stabilize the microscopic structure of the material upon heat-drying. This provides a potential solution to the problem of continuing structural changes, which take place with sol-gel materials long after the completion of their synthesis.