A critical analysis was carried out for the purpose of understanding the role of subcolloidal (nanosized) (alumino)silicate precursor species in the early stage of crystallization of zeolites in heterogeneous systems (hydrogels). The formation and evolution of these subcolloidal species in both the solid and the liquid phases were investigated by various experimental methods such a scanning electron microscopy (SEM, FE-SEM), transmission electron microscopy, atomic force microscopy, particle size analysis, pH measurement, atomic absorption spectroscopy, and dynamic light scattering, after careful separation of intermediates from reaction mixture by two-step centrifugation treatment. The results revealed that a chain of processes (i) the formation of low-molecular-weight (LMW) silicate species, by dissolution of Al-enriched amorphous silica, and their aggregation into about 3 nm sized primary precursor species (PPSs), (ii) the formation of larger (∼3 to ∼15 nm sized) silicate precursor species (LSPSs) by a rapid aggregation/coalescence of PPSs, (iii) the formation of “gel” (primary amorphous precursor) by a random aggregation of LSPSs at room temperature, and (iv) the formation of the worm-like particles (secondary amorphous precursor) occurred in the solid phase during heating of the reaction mixture (hydrogel) from room temperature to 170 °C. It is interesting that almost the same processes occur in the liquid phase but with decreased rate according to the relative low concentration of LMW silicate species. With the above described findings, it is highly expected that the manipulation of crystallization pathway through controlling the formation/evolution of precursor species in the initial stage of the process can be achieved.

Crystallization of zeolite ZSM-5 from a diluted heterogeneous system (12.5Na2O–Al2O3–8TPABr–60SiO2–4000H2O) was investigated by various experimental methods such as X-ray diffraction (XRD), electron diffraction (ED), infrared spectroscopy (FTIR), X-ray fluorescence (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), thermo-gravimetric analysis (TGA), particle size analysis (PSA), pH measurement, inductive coupling plasma (ICP) emission spectrometry, and dynamic light scattering (DLS). The crystallization process is characterized by a very long “induction period” (95% of the entire reaction time) and very fast transformation (5% of the entire reaction time) of amorphous to crystalline phase (zeolite ZSM-5) at the end of the crystallization process. Analysis of the obtained results has shown that the crystallization process takes place by a chain of processes: (i) formation of “primary” amorphous aluminosilicate precursor (gel) at room temperature, (ii) formation of “secondary” amorphous aluminosilicate precursor (“worm-like” particles, WLPs) at increased temperature (170 °C), (iii) formation of “tertiary” amorphous aluminosilicate precursor (condensed aggregates, CAs) by aggregation of the WLPs and densification (condensation) of aggregates, and (iv) formation of nuclei and their growth in the matrixes of CAs; these processes result in the formation of fully crystalline zeolite ZSM-5 in the form of polycrystalline aggregates.Keywords: condensed aggregates; heterogeneous system; polycrystalline aggregates; unusual crystallization pathway; zeolte ZSM-5; “worm-like” particles;

In this work, the influences of excess amount of sodium ions and the way/duration of ageing of the reaction mixture (hydrogel) on structural, particulate, morphological and chemical properties of the crystalline end products obtained by hydrothermal treatment (heating at 483 K for 2 h) of the TPA-free reaction mixture: 1.0Al2O3/100SiO2/xNa2O/4000H2O/yNa2SO4 (0.4 ⩽ (x + y) ⩽ 100) seeded by silicalite-1 nanocrystals (260 nm, 4 wt.% of silica in gel mixture), was investigated by different characterization methods such as, powder X-ray diffraction (XRD), scanning-electron microscopy (SEM), particle size distribution (PSD) measuring by laser light scattering (LLS) and X-ray fluorescence (XRF). The obtained results showed that addition of sodium sulfate in low-alkaline reaction mixture enhances the aggregation of the particles of colloidal silica and formation of gel by the action of sulfate oxy-anions while in high-alkaline reaction mixtures the condensation process takes place on the surface of the crystalline end products. Excess amount of sodium ions do not increase the crystallization rate thus showing that the rate-determining factor is concentration of “free” low-molecular weight silicate species, determined by the alkalinity of system. On the other hand, addition of sodium sulfate considerably reduces the formation of crystal aggregates, by combined chemical and electrical interactions. Ageing of the reaction mixture (hydrogel) mainly influences the particle size distribution of the crystalline end products, which is explained by the change in the relative rates of crystal growth and crystal aggregation with the time of ageing. However, hydrogel ageing does not affect the size and number of crystals in the crystalline end product, showing that the growth precursor particles form during hydrothermal treatment of the reaction mixture and not during its room-temperature ageing.Graphical abstractHighlights► Excess amount of batch sodium ion content behaves both the ‘oxy-anion’ and ‘cross-linking’ effect. ► The ageing of reaction mixtures decreases the aggregation tendency of the crystalline end products. ► The particulate properties of products largely depend on the batch sodium content and gel ageing.

In this work, the influence of alkalinity, A = [Na2O/H2O]b (b = batch), of the reaction mixture on structural, particulate, morphological and chemical properties of the crystalline end products obtained by hydrothermal treatment (heating at 483 K for 2 h) of the TPA-free reaction mixture: 1.0Al2O3/100SiO2/xNa2O/4000H2O seeded by silicalite-1 nanocrystals (260 nm, 4 wt.% of silica in gel mixture), was investigated by different characterization methods such as powder X-ray diffraction (XRD), scanning-electron microscopy (SEM), particle size distribution (PSD) measuring by laser light scattering (LLS) and X-ray fluorescence (XRF). The obtained results showed that, when silicalite-1 having the size of 260 nm was used as seed, fully crystalline product (silicalite-1/ZSM-5) having the size in the range of 400–600 nm and Si/Al ratio of 10–18 can be obtained for 0.006 ⩽ A ⩽ 0.01, in less than 2 h. However, the product obtained at low (A ⩽ 0.005) or high (A ⩾ 0.011) alkalinities possess amorphous and/or phillipsite impurities, respectively. The influence of alkalinity, A, on the mentioned properties of the crystalline end product was discussed in relation to the influence of alkalinity on the relevant critical process of zeolite ZSM-crystallization in the absence of organic templates.Graphical abstractResearch highlights► Low alkalinity, amorphous impurity, high Si/Al ratio with irregular particles of ZSM-5 zeolites. ► Medium alkalinity, pure ZSM-5 phase, decreasing Si/Al ratio with cubic particles. ► High alkalinity, phillipsite and amorphous impurity, low Si/Al ratio with spherical and irregular particles.