Pore Size Tailoring in Large-Pore SBA-15 Silica Synthesized in the Presence of Hexane

Abstract

Large-pore SBA-15 silicas were synthesized using poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) block copolymer Pluronic P123 as a template and hexane as a micelle expander. The reaction was initially carried out at 15 °C, followed by the heating of the synthesis gel at temperatures from 40 to 130 °C. Small-angle X-ray scattering data indicate that highly ordered two-dimensional hexagonal material (SBA-15 structure) formed at 15 °C and was preserved even after 5 days of heating at 130 °C. The unit-cell parameter for as-synthesized SBA-15 silicas was about 16.5 nm and increased only slightly after the heat treatment, whereas the unit-cell parameter after calcination was appreciably larger (16 vs 14 nm) for materials that were subjected to the thermal treatment. The pore size distribution of SBA-15 formed at 15 °C was narrow and centered at ∼9.5 nm, which is close to the upper limit of pore diameters typically reported for SBA-15. The presence of constrictions in the pores of this material was evident. The heat treatment led to the elimination of the constrictions and to the pore diameter increase to 15 nm or more, tailored by the selection of appropriate treatment temperature and time. The pore size increase was the fastest during the first day of treatment, but it continued for at least 5 days. The pore size distribution broadened as the time of the treatment increased beyond 1 day. The pore size increase appears to be primarily related to the decrease in the degree of shrinkage during the calcination (removal of the template) and the decrease in the pore wall thickness