We have found that the spontaneous formation of silica nanoparticles is a general phenomenon in basic solutions of small tetraalkylammonium (TAA) cations. The nanoparticle formation and structure have been investigated using conductivity, pH, and small-angle scattering methods. The particles have a core−shell structure with silica at the core and the TAA cations at the shell. The particle core size is nearly independent of the size of the TAA cation but decreases with pH, suggesting electrostatic forces are a key element controlling their size and stability. The nanoparticle formation is a reversible process at low temperatures, in several ways similar to surfactant aggregation into micelles. These silica nanparticles may be a connection between the synthesis of zeolites and ordered mesoporous silicas such as MCM-41.

The phase behavior of silica solutions containing organic and inorganic cations was studied at room temperature using conductivity, pH, and small-angle scattering experiments. A critical aggregation concentration (cac) was observed at approximately 1:1 ratio of SiO(2)/OH(-) for all cation solutions from conductivity and pH studies. From this cac, a phase diagram of the system was developed with three distinct phase regions in pseudoequilibrium: a monomer/oligomer region (I), a monomer/oligomer/nanoparticle region (II), and a gel region (III). Small-angle X-ray and neutron scattering (SAXS and SANS) on solutions of region II formed with tetrapropylammonium hydroxide (TPAOH) revealed that the nanoparticles have a core-shell structure. Structure analysis of the SAXS and SANS data was best fit by a core-shell oblate ellipsoid model. A polydisperse set of core-shell spheres also fit the data well although with lower agreement factors. Similar nanoparticle morphologies were found in solutions of TMAOH, CsOH, and NaOH.

Subcolloidal particles of a few nanometers in diameter are observed during the clear-solution synthesis of silicalite-1. These nanoparticles (3-5 nm) can be synthesized at room temperature starting from tetrapropylammonium (TPA) hydroxide, tetraethyl orthosilicate (TEOS), and water, and they have been reported to have a uniform structure identical to that of zeolite ZSM-5 (called nanoblocks or nanoslabs). To study their structure, we followed the extraction procedure proposed in the literature to obtain a dry powder of the particles. These dried particles were analyzed with powder X-ray diffraction (XRD), solid-state NMR spectroscopy, FTIR spectroscopy, thermogravimetric analysis, and N 2 adsorption isotherms. The results are compared with those obtained for colloidal size silicalite-1, amorphous silica, and the mesoporous silicate SBA-15. To obtain a better idea of the shape and structure of the particles, we conducted simulated annealing modeling to fit the particle shape to the fractions of Q n obtained from the 29 Si MAS NMR spectra. The model structures are in excellent agreement with our NMR data and suggest a poorly defined particle shape, in contrast to previous reports. The XRD patterns of samples with particle sizes in the range of the nanoparticles were simulated using the Debye formula and the SKIP algorithm. These simulations were carried out using structural models of silicalite-1 nanocrystals, the proposed nanoblock structure, and the silica particles derived from simulated annealing. We found no evidence in support of a well-defined MFI-like structure in the extracted material. The particles contain TPA, partly associated with the particles and partly as (TPA)Cl formed by the extraction process. The evidence accumulated here is in disagreement with the well-defined structure of the nanoparticles previously reported.

The microstructure of silica in basic aqueous solutions containing organic cations and prepared from monomeric precursors is reviewed and interpreted within the context of classical ideas of self-assembly of molecular aggregates. The solution properties can be understood by using the pseudo-phase separation approach coupled to the acid-base chemistry of silanol groups and the Poisson-Boltzmann equation. The silica nanoparticles frequently observed in these systems have a core-shell structure with silica in the core and the organic cations at the shell. Individual particles are observed when the forces between particles are repulsive-as is the case for small cations such as tetramethylammonium or tetrapropylammonium-and extended structures such as M41S materials are formed when the forces are attractive--as is the case for surfactants such as cetyltrimethylammonium. These ideas are useful to understand the evolution of zeolite synthesis gels from nucleation to crystal growth. Although at room temperature the silica and the organic cations are segregated, upon heating the organic cations are embedded within the particles. This transformation signals the onset of structure direction whereby the size and geometry of the organic cation induce changes in the structure of silica that may lead to zeolite nuclei.

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