Diffusion of redox probes in hydrated sol-gel-derived glasses. Effect of gel structure

The diffusion coefficients of redox probes entrapped in a silica matrix prepared by the sol-gel process were measured using a combination of cyclic voltammetry and chronoamperometry at an ultramicroelectrode. In this study, the porosities of the gels were varied to assess the importance of constrained environments vs intermolecular interactions on the translational mobility of guests entrapped in this solid host matrix. The average pore diameter of the gels was varied from 40 to 400 A by utilizing different catalysts (HCl, NH3, NaF) or different silicon precursors (tetramethoxysilane or Ludox colloidal silica). The diffusion coefficients of cobalt(II) tris(bipyridine), ferrocenemethyltrimethylammonium ion, and dicyanobis(phenanthroline)iron(II) and their rate of change as the gel dried were found to be nearly identical for gels prepared from TMOS and catalyzed with either HCl, NH3, or NaF. When trapped in gels prepared from Ludox, ferrocenemethanol and potassium ferricyanide diffused at rates identical to that measured in solution. In contrast, Dapp for ferrocenemethyl(trimethylammonium) dropped 1 order of magnitude over a 30-day drying period. These results attest to the importance of intermolecular interactions in governing diffusion in sol-gel-derived materials.