By inducing a phase separation parallel to the sol-gel transition of alkoxy
-derived silicate systems, gels with well-defined macroporous structure can
be prepared. Depending on the post-gelation treatment such as aging and so
lvent exchange, the final pore structure in the nanometer range of dried an
d heat-treated gels exhibits a considerable variation. With an aim of compl
etely controlling the hierarchical pore structure in the discrete size rang
es of nanometers and micrometers, systematic experimental studies have been
performed. The macroporous nature of the wet gels allows an efficient solv
ent exchange process compared with conventional gels only with mesopores. I
n addition, the surface chemistry of the wet gel skeleton affects the mesop
ore formation process by the solvent exchange to a great extent. The median
size of mesopores larger than 5 nm can be controlled by adjusting the basi
c solvent exchange conditions such as pH value, temperature and bath ratio
for any kind of macroporous silica gel. On the other hand, the control of p
ore volume independent of the mesopore size is possible only in the system
incorporated with the micelle-forming surfactant. Some examples of the effe
cts of controlled mesopores on the analytical performance of monolithic-typ
e chromatographic columns are also presented.