Family of Single-Micelle-Templated
Organosilica Hollow
Nanospheres and Nanotubes Synthesized through Adjustment of Organosilica/Surfactant
Ratio
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Abstract
A family of hollow organosilica nanospheres and nanotubes
was synthesized
at appropriately low organosilica-precursor/block-copolymer-surfactant
ratios. In Pluronic F127 (EO<sub>106</sub>PO<sub>70</sub>EO<sub>106</sub>) block copolymer templated synthesis of ethylene-bridged organosilicas
in the presence of a swelling agent, the lowering of the organosilica-precursor/surfactant
ratio led to a change from highly ordered face-centered cubic structure
of spherical mesopores to individual hollow spherical nanoparticles.
It was hypothesized that at low ratios of organosilica precursor to
PEO-PPO-PEO, the framework precursor is solubilized in the micelles
and its concentration on their surface is not sufficient to induce
appreciable cross-linking between the resulting nanoobjects and the
consolidation into larger particles. The inner pore size of the nanospheres
was adjusted by varying the micelle expander, allowing us to obtain
pore diameters up to ∼20 nm. By employing low precursor/surfactant
ratios, hollow spheres of methylene-, ethenylene-, and phenylene-bridged
organosilicas were synthesized. Hollow silica spheres were also obtained
through judicious choice of block copolymer. The synthesis strategy
involving the adjustment of the framework-precursor/surfactant ratio
was further extended on organosilica nanotubes synthesized using Pluronic
P123 surfactant and cyclohexane as a swelling agent. One can envision
a large number of framework compositions for which hollow nanospheres
and nanotubes can be obtained using our synthesis approach