A series of new mesoporous silica materials with MCM-41 type of structure containing a homogeneous layer of organic functional groups inside the pores was prepared using a cocondensation method under low surfactant concentration condition. This reproducible synthetic approach resulted in high surface coverage with several functional groups such as a primary amine, secondary amine, urea, isocyanate, vinyl, and nitrile. In addition, the presence of organoalkoxysilane precursors during the base catalyzed condensation greatly influenced the final particle shape. By changing the precursor or its concentration, the particle morphology was tuned to various shapes, including spheres, tubes, and rods of various dimensions. The synthetic procedures that gave rise to the specific particle morphologies were investigated and the mechanism responsible for shape control was postulated. The structure and functionality of these materials were characterized by field-emission scanning electron microscopy, transmission electron microscopy, solid-state NMR spectroscopy, thermogravimetric analysis, and nitrogen adsorption and desorption studies (BET isotherms and BJH pore size distribution measurements).

A systematic study of the surface of MCM-41-type mesoporous silica nanoparticles prepared under low surfactant concentration was carried out using high-resolution solid-state nuclear magnetic resonance spectroscopy. The structures and concentrations of various species present during dehydration and rehydration of mesoporous silicas between -25 and 500 degrees C were detailed by employing one-dimensional and two-dimensional (1)H, (13)C, and (29)Si NMR, including (1)H signal intensity measurements, (1)H-(1)H homonuclear correlation experiments (double quantum, exchange, and RFDR), and (1)H-(29)Si heteronuclear correlation NMR. These experiments employed high MAS rates of up to 45 kHz. The study shows that the surfactant (CTAB) was almost completely removed by acid extraction. The residual molecules assumed prone positions along the pores, with the tailgroup being most mobile. The weakly adsorbed water was hydrogen bonded to the silanol groups, all of which were involved in such bonds under ambient humidity. Specific structures involving water and silanol groups were proposed for various stages of thermal treatment, which included dehydration, dehydroxylation, and subsequent rehydration.