FDU-1 silicas with large cage-like pores (diameter about 10 nm) were synthesized under acidic conditions from tetraethyl orthosilicate in the presence of a poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer template B50-6600 (EO(39)BO(47)EO(39)). High-resolution transmission electron microscopy and small-angle X-ray scattering provided strong evidence that FDU-1 silica synthesized under typical conditions is a face-centered cubic Fm3m structure with 3-dimensional hexagonal intergrowth and is not a body-centered cubic Im3m structure, as originally reported. Samples synthesized in a wide range of conditions (initial temperatures from 298 to 353 K; hydrothermal treatment at 333-393 K) exhibited similar XRD patterns and their nitrogen adsorption isotherms indicated a good-quality cage-like pore structure. The examination of low-pressure nitrogen adsorption isotherms for FDU-1 samples, whose pore entrance diameters were evaluated using an independent method, allowed us to conclude that low-pressure adsorption was appreciably stronger for samples with smaller pore entrance sizes. This prompted us to examine low-pressure adsorption isotherms for a wide range of samples and led us to a conclusion that the FDU-1 pore entrance size can be systematically enlarged from about 1.3 nm (perhaps even lower) to at least 2.4 nm without an appreciable loss of uniformity by increasing the temperature of the hydrothermal treatment or the initial synthesis. Further enlargement of pore entrance size was achieved for sufficiently long hydrothermal treatment times at temperatures of 373 K or higher, as seen from the shape of nitrogen desorption isotherms. This allowed us to obtain samples with uniform pore sizes, high adsorption capacity, and with pore entrances enlarged so much that their size was similar to the size of the pore itself, resulting in a highly open porous structure. However, in the latter case, there was evidence that the pore entrance size distribution was quite broad.

After the recent discovery of periodic mesoporous organosilicas (PMOs), 1-4 their synthesis, reactivity, structural characterization, and prospective applications have received much attention. [5][6][7][8][9][10][11][12][13][14] PMOs were already found to be promising as catalysts, 11 templates for nanostructure synthesis, 12 and selective adsorbents. 14 There is currently a quest for expanding the pore size domain attainable for PMOs 15-18 because large-pore PMOs are of kin interest from the point of view of immobilization and encapsulation of large molecules. 17,18 Standard PMO synthesis using alkylammonium surfactants affords pore diameters below about 5 nm, [1][2][3][4] and pore diameters of PMOs templated by neutral amines 19 and oligomeric surfactants 9,[19][20][21][22] were also found to be below this limit. 9,19 So the only large-pore