A silanol-free
silica with high surface area was prepared by postfunctionalization
of silica by means of sol–gel reaction with triethoxysilane
followed by a high-temperature dehydroxylation treatment. Besides
the absence of surface silanols, paramagnetic and diamagnetic defect
sites are generated according to UV–vis, electron paramagnetic
resonance (EPR), and reactivity studies. The diamagnetic defects are
assigned to oxygen-deficient Si centers (silylenes), which exhibit
a distinct UV–vis signature and reactivity. The paramagnetic
defects are attributed to silicon-centered radicals that display particularly
high g values in EPR compared to reports of commonly
described silicon radicals in silica (E’ sites), suggesting
the presence of a silicon atom in its proximity. These defect sites
are highly reactive and generate dihydrosilane, a silane radical,
a peroxyl radical, and methylsiloxane upon reaction with dihydrogen,
dioxygen, and methane, respectively.