Heteroatom incorporation, zeolite

Heteroatoms (B, Al, Fe, Ga, and Ti) may be incorporated into the framework of high-silica and all-silica materials in the presence of fluoride as well, giving rise to active acid catalysts. Usually, transition metal ions will hydrolyse to form hydroxide or oxide precipitates in a high-pH solution. Therefore, there is a limitation to the content of transition metals in heteroatom-substituted zeolites. However, this limitation can be significantly increased by using fluoride during the synthesis because fluoride can coordinate to the transition metal atoms to form stable complex, which will help transition metal atoms incorporate into the framework of zeolites. 

AODITY AND THE INCORPORATION OF HETEROATOMS INTO ZEOLITE FRAMEWORKS... 

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. 

The other way to introduce heterometals is their isomorphous substitution for Si in the framework, in a similar manner to the isomorphous substitution of Al. The heteroatoms should be tetrahedral (T) atoms. In hydrothermal synthesis, the type and amount of T atom, other than Si, that may be incorporated into the zeolite framework are restricted due to solubility and specific chemical behavior of the T-atom precursors in the synthesis mixture. Breck has reviewed the early literature where Ga, P and Ge ions were potentially incorporated into a few zeolite structures via a primary synthesis route [9]. However, until the late 1970s, exchangeable cations and other extraframework species had been the primary focus of researchers. 

Since the incorporation of transition metals into the frameworks of zeolites or micro-porous ahiminophosphates to form heteroatom-containing molecular sieves with important application values, the synthesis, structure, and characterization of microporous transition metal phosphates have been extensively studied in the last decade. In particular, because transition metal cations possess redox and coordination features, they are a kind of catalytic material with useful applications, and promise potential... 

The local structures of Zn (II) and Fe (III) in the lattice framework of mordenites have been characterized by means of X-ray Absorption Fine Structure. The main absorption structure of the XANES reveals the covalent bonding between the heteroatom and the lattice oxygen atom. The pre-edge structure appeared in XANES spectra of (Si, Fe)-MOR suggests a tetrahedral structure of Fe, which confirms the incorporation of Fe into the zeolite framework. Furthermore, the tetrahedral structure of the heteroatoms in the framework and their coordination distances are determined by using EXAFS technique. 

The variability in chemical composition of silicate zeolites is just amazing. Considering first just the framework, the number of heteroatoms i.e. atoms other than Si that can occupy tetrahedral positions in the framework) that have been (or have been claimed to be) incorporated into zeolites is formidable Al, Ga, Fe, Fe " ", Co " ", Be, ... 

Zeolites are crystalline aluminosiHcates. Their unit cells are quite complex, as they have intricate microporous structures. Currently, around 200 frameworks are known for zeolites [10], and they all have one specific characteristic chaimels and pores in the size range 2 A to 1 nm, incorporated into the framework structure. This characteristic makes them appropriate for use as, for example, molecular sieves, cation-exchange materials, supports for catalytic active phases, and catalysts themselves [11, 12]. Controlled synthesis of zeoHte materials is still a challenge, and in this regard only a few selected zeolites have been studied in detail [13]. Silicalite-1 (MFI framework) has a pure-silica stmcture, but does not have active sites. The incorporation of, for example, heteroatoms such as aluminum (ZSM-5) makes it catalytically active [14, 15]. Nevertheless, silicalite-1 can be seen as an archetype system, of which its preparation has been characterized in great detail. 

The assessment of true incorporation of the heteroatom in a zeolite framework assumes paramount importance. In fact, the physico-chemical and catalytic properties of the materials strictly depend on the location of heteroatoms in framework sites. This is particularly true for titanium it is well known that a dramatic difference in catalytic performance exists between a well synthesized TS-1 sample and one containing extra-framework titanium species. 

The preceding examples demonstrate that the incorporation of heteroatoms in the aluminophosphate frameworks can stabilize the zeolite framework and induce novel zeotype structures. 

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