Formation mechanism and size control in one-pot synthesis of mercapto-silica colloidal spheres

Mercapto-silica spheres with controllable size from ∼150 nm to ∼3.5 μm and narrow size distribution have been prepared in water using a one-pot synthesis, in which 3-mercaptopropyltrimethoxysilane (MPS) was used as the sole silica source and ammonia as the base catalyst. The hydrolysis of MPS at the early stage of the reaction produces amphiphilic silicate species which initiate the self-emulsification of the system and lead to the formation of oil-in-water emulsion droplets. Further hydrolysis and condensation promote the nucleation and growth of the mercapto-silica spheres inside the emulsion droplets. These mercapto-silica spheres are both structurally and functionally different from typical silica particles prepared from silicon alkoxides. Understanding the formation mechanism allows systematic tuning of the size of mercapto-silica spheres in a wide range by changing the amount of precursor, the concentration of ammonia, the amount of additional surfactants, and the reaction time. We find that Ostwald ripening may occur quickly if the spheres are kept in the reaction solution, resulting in significant broadening of the particle size distribution. In order to obtain uniform and stable samples, it is important to quench the growth of the mercapto-silica spheres by separating them from the original reaction mixture and then storing them in solvents that can prevent further ripening.