Post-synthesis method

A different approach to the substitution of metal atoms into the framework is the secondary synthesis or post-synthesis method. This is particularly effective in synthesizing metallosilicates that are difficult to crystallize from the gels containing other metal atoms or hardly incorporate metal atoms by the direct synthesis method. Substitution of Ti for A1 goes back to the 1980s. The reaction of zeolites with an aqueous solution of ammonium fluoride salts ofTi or Fe under relatively mild conditions yields materials that are dealuminated and contain substantial amounts of either iron or titanium and are essentially free of defects [58]. However, no sufficient evidence for the Ti incorporation has been provided. 

As a totally different post-synthesis method that is firmly based on the structural charaderistics of MWW, reversible strudural conversion between 3D MWW silicate and its corresponding 2D lamellar precursor MWW (P) has been developed to construd more active Ti species within the framework [24, 70], Figure 4.7 illustrates the strategy of this post-synthesis method of reversible strudural conversion. First, highly siliceous MWW is prepared from hydrothermally synthesized MWW boro-silicate by the combination of caldnation and acid treatment. Second, the MWW silicalite is treated with an aqueous solution of HM or PI and a Ti source. A reversible structure conversion from MWW into the corresponding lamellar precursor occurs as a result of Si-O-Si bond hydrolysis catalyzed by OH, which is supplied by basic amine molecules. This is accompanied by the intercalation of the amine molecules. 

Post-synthesis methods (pore-size engineering) allow an existing shape-selectivity effect to be intensified, and also a new one to be established. However, normally not only the pore size will be influenced by most of these methods, but also the catalytic activity. Vansant [104] gives a classification of post-synthesis modification methods which covers the entire range of zeolite applications (gas separation, gas purification, encapsulation of gases and catalysis). 

Post synthesis methods were also proposed to incorporate metals into various structures Purely aluminosilicate zeolites were chemically treated with a variety of compounds including P(0CH3)3, H3BO3, H3PO4 (17,18), metal halides and/or oxides, as well as ammonium fluorometallates (19). As a result, modifications of the framework and non framework features could occur separately or simultaneously. 

Niobium and tantalum were incoiporated into the faujasite aluminosilicate structure in one-pot synthesis and also by post-synthesis method, i.e. sohd-state ion exchange. One-pot synthesized zeolites exhibit Nb and Ta incorporated into the zeolite skeleton as evidenced by different methods. The efficiency of metal incorporation examined by XPS measurements was found to be higher for tantalum than for niobium. 

Location of transition metals in the framework and extra framework positions can be deduced from their coordination. Tetrahedrally coordinated species should be detected for framework position, whereas the octahedral coordination can point to the extra framework ones. The UV-Vis spectra of the samples prepared in the one-pot syrrlhesis show the bands characteristic of tetrahedrally coordirrated trarrsition metals, especially for the tantalum containing samples in which the efficiency of metal incorporation was higher (see Table 1). Moreover, the spectra of these samples differ from those recorded for materials prepared via post-synthesis modification. Figure 2 presents the UV-Vis spectra of tantalum oxide, and tantalum incorporated into Y zeolite by synthesis and post-synthesis methods. It is clearly seen, that the latter technique leads to the formation of octahedrally coordinated species, which is likely to be bulk tantalum oxide. However, in the one-pot synthesis method all tantalum is characterized by a band at c.a. 221 nm, typical of tetrahedrally coordinated Ta species. Therefore, one can conclude about the location of Ta in the zeolite skeleton. 

The Ti was loaded using two methods direct incorporation into the synthesis mixture, and post-synthesis grafting. In all cases the Ti-loading was 1.5 -1.8 wt%. Selectivity towards the epoxide was always 100%. Table 41.1 summarizes the results comparing Ti-TUD-1 and Ti-MCM-41 for cyclohexene epoxidation (15). For the direct incorporation, Ti-TUD-1 is five times more active than Ti-MCM-41, even though they have equivalent surface area. However, the grafted MCM-41 is also more active than its as-synthesized counterpart. 

This indicates that post-synthesis modification of MOFs by coordinating hydrophobic ligands to unsaturated metal sites may be a powerful method to generate new sorbents for gas separation under humid conditions. Amine functionalization to target the water stability of MOFs will be further discussed in the next section. 

Purely siliceous SBA-15 was synthesized according to previously published method [2]. Al incorporation in SBA-15 lattice was performed either by direct synthesis for which we have applied an already known method, but improved in some details [3], or by post-synthesis according to the reported procedure [4, 5], Modified SBA-15 are denoted as Al-SBA-15. 

Deleuze et al. used the same approach for the synthesis and functionalization of emulsion-derived polymeric foams [119]. Alternatively, a post-synthesis grafting method recently developed in our group offers access to high-capacity functionalized monolithic systems. Such high capacity monoliths are vital to various applications such as catalysis, extraction of environmental contaminants, extraction of biochemicals for either pharmaceutical or clinical purposes or, more generally, separation techniques [100]. With these systems, amounts of grafted monomers can exceed 1 mmol/g [94]. 

Substitution of silicon by other atoms like Ti or Al was reported to improve the thermal and hydrothermal stability to some extent [6]. It was also reported that improved hydrothermal stability could be achieved by adjusting the gel pH several times during crystallization process [7], Post-synthesis silylation technique has also been reported to enhance the hydrothermal stability of mesoporous materials by increasing the hydrophobicity of the samples [8,9]. However, it is most desirable to develop a method for preparing hydrother-mally stable mesoporous material by direct synthesis route. 

Niobium and titanium incorporation in a molecular sieve can be achieved either by hydrothermal synthesis (direct synthesis) or by post-synthesis modification (secondary synthesis). The grafting method has shown promise for developing active oxidation catalyst in a simple and convenient way. Recently, the grafting of metallocene complexes onto mesoporous silica has been reported as alternate route to the synthesis of an active epoxidation catalyst [21]. Further the control of active sites, the specific removal of organic material (template or surfactant) occluded within mesoporous molecular sieves during synthesis can also be important and useful to develop an active epoxidation catalyst. Thermal method is quite often used to eliminate organic species from porous materials. However, several techniques such as supercritical fluid extraction (SFE) and plasma [22], ozone treatment [23], ion exchange [24-26] are also reported. 

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. 

Materials obtained from the LDH show a reduction in SSA with the temperature as reported in the literature. This reduction can be attributed to the crystallisation of the material [15,17]. However, post-treatment with mineral acid was an increase in the SSA for all temperatures. It is possible to attribute this increase to two combined effects, which can both increase the porosity of the materials, as well as yield more active adsorption sites (i) the elimination of ZnO and (ii) the elimination Zn(II) cations occupying octahedral sites in the spinel oxide structure. Even though the SSA had varied sensibly, the average pore size (APS) remained fairly constant with temperature. Acid treatment increases the APS value for all temperature tested, although the effect was very small (Figure 5b). Comparison of the materials obtained by the different synthesis methods showed that spinel oxides obtained from the LDH presented greater SSA values than those obtained by other methods, principally after the posttreatment with mineral acid. On other hand, the treatment with acid had little influence on the textural properties of the spinel oxides obtained by the other methods. 

Post-synthesis gas-solid isomorphous substitution methods are also known [61]. Ti-beta essentially free of trivalent metals can be prepared from boron-beta. However, the gas-phase method is not efficient for Ti incorporation and could have some disadvantages such as the deposition of Ti02 [62],... 

Post-synthesis modifications have been successful in preparing titanium-containing molecular sieves active in oxidation. The method employed for the post-synthesis incorporation of Ti to the zeolite beta was also applied to the incorporation of Ti into MOR and FAU [60]. 

Direct synthesis of metal-substituted zeolites has long been sought. However, since the post-synthesis modifications can be made under wide-ranging conditions (temperature, solvent, atmosphere, pH, etc.) far from those for the zeolite synthesis, the modifications of zeolites present us with powerful indirect methods for manipulating the properties of zeolites. Therefore, the fine-tuning of the properties of zeolites will continue to be achieved by developing various post-synthesis modification procedures as well as direct synthetic techniques. 

---