The formation and consumption of nanometer scale precursor particles during the hydrothermal synthesis of Si-TPA-MFI from a clear solution has been studied in situ using a combination of X-ray scattering techniques and with electron microscpy. The combination of wide-, small-, and ultra-small-angle X-ray scattering allowed us to obtain information on a continuous range of length scales spanning over four orders of magnitude (0.17−6000 nm), covering all particle populations present during the complete course of the crystallization process. The use of high-brilliance synchrotron radiation allows us to perform time-resolved experiments. Two types of precursor particles were observed:  2.8 nm sized primary units and aggregates (≈10 nm). Variation of the alkalinity of the synthesis mixture revealed a strong correlation between the concentration of the aggregates and the rate of the crystal nucleation. The presence of the 2.8 nm sized primary units appears to be independent on the alkalinity. The addition of seed crystals to a synthesis mixture that does not show spontaneous nucleation (no aggregates observed) resulted in normal crystal growth. The size distribution of the growing crystals could be followed in situ by fitting calculated scattering patterns to experimental curves and showed good agreement with electron microscopy results. The apparent activation energy for crystal growth is determined to be 83 kJ/mol by following in situ the crystal growth process at various reaction temperatures. These data show that the formation of aggregates of primary units is an essential step in the nucleation process and suggest that the crystal growth step is the reaction-controlled inclusion of the 2.8 nm sized primary units at the crystal surface.

The formation of precursors and the growth and aggregation of silicalite-1 crystals using tetrapropylammonium as a template (Si-TPA-MFI) has been studied in situ using X-ray scattering techniques. Simultaneous smallangle and wide-angle X-ray scattering (respectively SAXS and WAXS) experiments using synchrotron light showed that the formation of amorphous colloidal aggregates in water clear synthesis mixtures was dependent on the alkalinity of the solutions. In situ time-resolved ultra-small-angle X-ray scattering (USAXS) showed the form factor oscillations of the growing crystals. Fitting of the USAXS patterns to the scattering pattern of spherical particles having a normal particle size distribution showed a linear growth of the average crystal diameter, which was approximately the same for both alkalinities studied. The final size of the crystals was highest for the synthesis mixture having the highest alkalinity, which can be explained in terms of number of viable nuclei formed. At the end of the linear growth the crystals form aggregates corresponding with a diffusion limited aggregation process (mass fractal dimension of 1.8).

The correlation between the formation of colloidal aggregates and the crystallization of silicalite-1 from a clear solution has been investigated with in situ combined small-angle X-ray scattering and wide-angle X-ray scattering, and in situ ultra-small-angle X-ray scattering using synchrotron radiation. Increasing the aging time at room temperature of the synthesis mixture prior to heating to the reaction temperature reduced the induction period and increased the crystal growth rate without affecting the formation of colloidal aggregates. Dilution of the synthesis mixtures did not influence the nucleation and crystal growth rate, and did not affect the formation of colloidal aggregates.

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