The sol–gel process enables the preparation of silica-based matrices with tailored composition and properties that can be used in a variety of applications, including catalysis, controlled release, sensors, separation, etc. Commonly, it is assumed that silica matrices prepared via the sol–gel synthesis route are “inert” and, therefore, do not affect the properties of the substrate or the catalyst. This short review points out that porous silica affects the properties of adsorbed/entrapped species and, in some cases, takes an active part in the reactions. The charged matrix affects the diffusion of ions, thus affecting catalytic and adsorption processes. Furthermore, recent results point out that ≡Si-O. radicals are long-lived and participate in redox processes. Thus, clearly, porous silica is not an inert matrix as commonly considered.
