Study of zeolite synthesis

Spectroscopic Studies of Zeolite Synthesis Evidence for a Solid-State Mechanism... 

The theoretical work to be discussed here has been initiated with the aim of providing support to fundamental studies of zeolite synthesis. Central to our discussion is the question whether a synthesis approach for new zeolites can be developed on the basis of guidelines generated by computational design. 

B.D. McNicol, G.T. Pott, and K.R. Loos. Spectroscopic Studies of Zeolite Synthesis Evidence for a Solid-state Mechanism, in Molecular Series . Adv. Chem. Ser., 1973, 121, 152-161. 

SAXS measurements are normally performed in situ and therefore require access to synchrotron radiation [21, 23, 27, 46]. SAXS is probably one of the most used in situ techniques for the study of zeolite synthesis. In situ cells, similar to those for WAXS or XRD measurements, can easily cope with elevated synthesis temperatures and pressures. It has been used to determine the activation energy of nucleation, where two independent studies show that it is around 70-85 kj mol [47, 48]. Also, three distinct particle sizes were observed in the reaction mixtures, being primary units of approximately 2.8 nm, their aggregates, and the actual zeolite crystals [47]. Other mechanistic studies include the effect of the precursor molecule, the chemical nature of which appears to be important in... 

An alternative hypothesis, developed from studies of the synthesis of Linde A zeolite carried out by Kerr (5) and Ciric (6), pointed to growth occurring from solution. The gel was believed to be at least partially dissolved in solution, forming active aluminosilicate species as well as silicate and aluminate ions. These species linked to form the basic building blocks of the zeolite structure and returned to the solid phase. Aiello et al. (7) followed the synthesis from a highly alkaline clear aluminosilicate solution by electron microscopy, electron diffraction, and x-ray diffraction. These authors observed the formation of thin plates (lamellae) of amorphous aluminosilicates prior to actual crystal formation. 

It is well known that the elements in framework of zeolite molecular sieves greatly influence the properties and behaviors of these materials [1-3], The introduction of heteroatoms into the framework has become one of most active fields in study of zeolites. The investigations were mostly focused on the methods to introduce heteroatoms into the framework (for examples, hydrothermal synthesis and post-synthesis), the mechanisms for incorporations, the effect of heteroatoms on the acid-base properties and the catalytic features of modified samples [1-10]. Relatively less attention was paid to the effect of treatment process on the porous properties of samples although the incorporation of heteroatoms, especially by the so-called post-synthesis, frequently changes the distribution of pore size. Recently, we incorporated Al, Ga and B atoms into zeolites (3 by the post-synthesis in an alkaline medium named alumination, galliation and boronation, respectively. It was found that different trivalent elements inserted into the [3 framework at quite different level. The heteroatoms with unsuitable atom size and poor stability in framework were less introduced, leading to that a considerable amount of framework silicon were dissolved under the action of base and the mesopores in zeolite crystal were developed. As a typical case, the boronation of zeolites (3 and the accompanied formation of mesopores are reported in the present paper. 

While silicate and aluminate solutions have been extensively studied using 29Si and 27A1 NMR (see Sections III,B and III,I, respectively), there is only a handful of publications that investigate mixed (Si,Al)-bearing solutions by NMR spectroscopy with a view to elucidating the mechanism of zeolite synthesis. There is thus a considerable scope for further work in this important area. 

The study of alkaline silicate and aluminosilicate solutions is of fundamental importance for a better understanding of the mechanism of zeolite synthesis (1,2). Real progress has been realized durinq the last fifteen years thanks to the use of new techniques such as the trimethylsilylation (3,4) of polysilicic acids (followed by a chromatographic separation of the derivatives) and, even more, 29Si and 27Ai NMR spectroscopy (5-11). The latter techniques have enabled the identification of about twenty types of oligomers in silicate solutions and in some cases estimates of their respective concentrations. The investigation of alkaline aluminosilicate solutions is... 

J. Bronic, P. Frontera, F. Testa, B. Subotiae, R. Aiello, and J.B. Nagy, Study of Zeolite A Crystallization from Clear Solution by Hydrothermal Synthesis and Population Balance Simulation. Stud. Surf. Sci. Catal., 2001, 135 (Zeolites and Mesoporous Materials at the Dawn of the 21st Century), 358-365. 

Just like IR spectroscopy, Raman can detect small. X-ray amorphous zeolite particles. Therefore RWan has been used to examine both the liquid and the solid phase of zeolite synthesis mixtures [28], Ex situ methods (with separation of solid and liquid) and in situ methods have been applied. In studying the liquid phase [10-11], one should remember that (i) minimum concentrations for detection of spontaneous Raman from liquids are typic ly 0.05 - 0.1 M, [15-27, 29] (ii) that the cross-section of the Al(OH)4 species is much stronger than e.g. for silicate or aluminosilicate anions [30]. Thus species which are present in low concentration or with variable structures may easily be overlooked in Raman spectra of the synthesis liquors. 

STUDIES OF ZEOLITE AND ZEOTYPE CRYSTALLISATION A STEP-BY-STEP DESCRIPTION OF THE SYNTHESIS PROCESS... 

Density functional methods is an attractive alternative to Hartree Fock method due to its computational efficiency. There are density functional methods with different correlation functions [42-48]. Recently several calculations [49-53] were done on zeolites of varying cluster models with density functional methods. Periodic density functional method similar to periodic Hartree Fock is also being used recently [54]. Thus the quantum chemical technique has been at the center stage among the other computational methods in improving our understanding of stmeture and reactivity of zeolites. We apply this powerful technique to study the mechanism of zeolite synthesis. 

P-29 - Study of zeolite A crystallization from clear solution by hydrothermal synthesis and population balance simulation... 

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