The recently discovered mesoporous aluminosilicate MCM-41 consists of hexagonal arrays of nanometer-sized cylindrical pores. It is shown that this material can be synthesized by cooperative condensation of silicate and cylindrical cationic micelles. Careful control of the surfactant-water content and the rate of condensation of silica at high alkalinity resulted in hollow tubules 0.3 to 3 micrometers in diameter. The wall of the tubules consisted of coaxial cylindrical pores, nanometers in size, that are characteristic of those of MCM-41. The formation of this higher order structure may take place through a liquid crystal phase transformation mechanism involving an anisotropic membrane-to-tubule phase change. The hierarchical organization of this "tubules-within-a-tubule" particle texture is similar to that of the frustules of marine diatoms.
A formal derivation is presented for the equilibrium relation between the singlet density in a fluid and the direct correlation function and for the equivalent relation involving the pair number density. It is shown that this relation is equivalent to the macroscopic condition for hydrostatic equilibrium when the singlet density varies sufficiently slowly to permit the introduction of local thermodynamics. Some aspects of the usage of this in the determination of the singlet density in the liquid–vapor transition region are discussed.
Mesoporous MCM-41 materials with a distinct N 2 -sorption hysteresis behavior have been prepared from pure silica and aluminosilicate-C 16 trimethylammonium (TMA)Br systems by a delayed neutralization procedure. On the basis of the analysis of transmission electron microscopy micrographs of these MCM-41 materials, we observed that the sample with large type-H4 hysteresis loop at p/p 0 between 0.5 and 1.0 contains extensive structural defect holes amid the nanochannels. These holes are irregular in shape and their size distributes between 5.0 and 30.0 nm. The pore-blocking effect leads to the hysteresis in desorption. Aluminosilicate MCM-41 often possesses a larger hysteresis loop than pure silica MCM-41. The linear channel system of MCM-41 becomes effectively interconnected through these defect holes. The unusual adsorption hysteresis is associated with the pore-blocking effect around the embedded voids in the framework structures. The size of the adsorption-desorption hysteresis loop is proportional to the volume of hole defects in the nanochannels, and it is dependent on the synthesis conditions such as water content, Si/Al ratio, and morphology. Tubular morphology is often associated with large hysteresis behavior and thus more hole defects. The interconnecting channels through defect holes thus makes the diffusion of molecules inside the MCM-41 structure more effective, which is important in catalysis applications.
Mesoporous silica materials with well-ordered hexagonal structure were synthesized under acidic conditions by using various acid sources HX. The induction time for the formation of mesostructural precipitation increases in the lyotropic series HNO 3 < HBr < HCl < H 2 SO 4 under the same acid concentration. The induction rates are analyzed with a micelle-catalyzed reaction scheme. The order in induction time reflects the strength in counterion binding of X -. Nitric acid with the highest binding strength of counterion tends to form very long micelles. We have determined the counterion association constants and found the degree of counterion dissociation under synthetic conditions in solution. The association is only partial during the early morphologysetting stage. HNO 3 is a suitable acid source for preparing silica ropes of hierarchical order, consisting of silica fibers formed from parallel nanosized channels. The elongation of the surfactant micelles and shearing flow are the controlling factors in the morphology. Temperature, acid concentration, surfactant chain length, and the addition of polar solvent also have strong influence on the morphology and nanostructure of the mesoporous materials under acidic conditions.
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