The silica (SiO2) nanoparticles
of a well-known silica
precursor tetraethyl orthosilicate (TEOS) are generally synthesized
via a promising solution-gelation inorganic polymerization process.
The monodisperse silica nanoparticles have potential applications
ranging from the formation of dental nanocomposites to antireflective
coatings. In the present study, we have systematically investigated
the in situ interfacial molecular structure of TEOS and its impact
on the interfacial water structure during the processes of hydrolysis
and condensation at the air–aqueous interface using sum-frequency
generation (SFG) vibrational spectroscopy. With the presence of water,
a gradual decrease in the SFG intensity in the CH-stretch region for
each concentration of TEOS with time reflects the elimination of ethoxy
groups, which is a signature of the hydrolysis process. Further, the
impact of the hydrolysis process is revealed from the significant
enhancement in the SFG signal in the OH-stretch region. The hydrolysis
of TEOS is then followed by condensation in which the SiO– charged species are replaced by forming the SiOSi
bridging network. The signature of the condensation process is reflected
with the gradual decrease in the observed enhanced SFG signal in the
OH-stretch region. The formation of monodispersed silica nanoparticles
as an end product of size variation from 1.75 to 4.67 nm with the
increase in TEOS concentration is confirmed with the DLS measurements.
We have also probed the pH-dependent SFG studies at three different
pH values (2.0, 5.8, and 9.0). The dominant pH-dependent hydrolysis
process is revealed from the observed molecular structure of TEOS
at the air–aqueous interface.