In 1999 Cédric Boissière and his team developed a two-step process whereby the hydrolysis at low pH (1 – 4) is completed before the condensation reaction is initiated by the addition of sodium fluoride (NaF). The two-step procedure includes the addition of a nonionic surfactant template to ultimately produce mesoporous silica particles. The main advantage of sequencing the hydrolysis and condensation reactions is the ability to ensure complete homogeneity of the surfactant and the precursor TEOS mixture. Consequently, the diameter and shape of the product particles as well as the pore size are determined solely by the reaction kinetics and the quantity of sodium fluoride introduced; higher relative fluoride levels produces a greater number of nucleation sites and hence smaller particles. Decoupling the hydrolysis and condensation process affords a level of product control that is substantially superior to that afforded by the one-step Stöber process, with particle size controlled nearly completely by the sodium fluoride-to-TEOS ratio.
The two-step Stöber process begins with a mixture of TEOS, water, alcohol, and a nonionic surfactant, to which hydrochloric acid is added to produce a microemulsion. This solution is allowed to stand until hydrolysis is complete, much like in the one-step Stöber process but with the hydrochloric acid replacing the ammonia as catalyst. Sodium fluoride is added to the resulting homogeneous solution, initiating the condensation reaction by acting as nucleation seed. The silica particles are collected by filtration and calcined to remove the nonionic surfactant template by combustion, resulting in the mesoporous silica product.
The selection of conditions for the process allows for control of pore sizes, particle diameter, and their distributions, as in the case of the one-step approach. Porosity in the modified process is controllable through the introduction of a swelling agent, the choice of temperature, and the quantity of sodium fluoride catalyst added. A swelling agent (such as mesitylene) causes increases in volume and hence in pore size, often by solvent absorption, but is limited by the solubility of the agent in the system. Pore size varies directly with temperature, bound by the lower out of the surfactant cloud point and the boiling point of water. Sodium fluoride concentration produces direct but non-linear changes in porosity, with the effect decreasing as the added fluoride concentration tends to an upper limit.