Access to Ultralarge-Pore Ordered Mesoporous Materials through Selection of Surfactant/Swelling-Agent Micellar Templates

The surfactant-micelle-templating method has revolutionized the synthesis of high-surface-area materials with mesopores (diameter 2-50 nm) that have well-defined shapes and sizes. One of the major benefits of this method is the ability to tailor the pore size by manipulating the size of the templating micelles. The uniform pores typically form ordered arrays. Although the choice of surfactant can tune the size of the micelles, it is more convenient to use a single surfactant and tailor the micelle size by adding a swelling agent. Unfortunately, the swelling agent tends to induce disorder or heterogeneity in the resulting structures, which can make this approach difficult to implement. We hypothesized that the swelling agents that are moderately solubilized within the micelles of a particular surfactant could generate well-defined micelle-templated structures with significantly enlarged pores. Using this idea, we could judiciously select candidate swelling agents from families of compounds whose extent of solubilization in the surfactant micelles systematically changes with variations in the compound structure. Alkyl-substituted benzenes proved very useful as swelling agents, because their extent of solubilization in micelles of common Pluronic surfactants (EO(m)PO(n)EO(m); EO = ethylene oxide, PO = propylene oxide) significantly increases as the number or size of alkyl substituents decreases. On the basis of these principles, we identified 1,3,5-triisopropylbenzene and cyclohexane as swelling agents for the synthesis of ultralarge-pore SBA-15 silica (pore diameter up to 26 nm) and organosilicas with 2-D hexagonal structures of cylindrical mesopores. Moreover, we used xylene, ethylbenzene, and toluene as swelling agents for the synthesis of large-pore (pore diameter up to 37 nm) face-centered cubic silicas and organosilicas with spherical mesopores. During the early stages of the synthesis, the entrances to large cylindrical and spherical mesopores of these materials were much smaller than the inner pore diameter. Therefore we can often use calcination at sufficiently high temperatures (400-950 °C) to produce closed-pore silicas. Using hydrothermal treatments, we can obtain materials with large pore entrance sizes. In Pluronic-templated synthesis, we observed the propensity for formation of single-micelle-templated nanoparticles as the ratio of the framework precursor to surfactant decreased, and this process afforded organosilica nanotubes and uniform hollow spheres with inner diameters up to ∼21 nm. Consequently, the adjustment of variables in the micelle-templated synthesis allows researchers to tailor the pore size and connectivity and to form either periodic pore arrays or individual nanoparticles.