Mesoporous molecular sieves, structural silicates

In the present work the synthesis of highly dispersed niobium or titanium containing mesoporous molecular sieves catalyst by direct grafting of different niobium and titanium compounds is reported. Grafting is achieved by anchoring the desired compounds on the surface hydroxyl groups located on the inner and outer surface of siliceous MCM-41 and MCM-48 mesoporous molecular sieves. Catalytic activity was evaluated in the liquid phase epoxidation of a-pinene with hydrogen peroxide as oxidant and the results are compared with widely studied titanium silicalites. The emphasis is directed mainly on catalytic applications of niobium or titanium anchored material to add a more detailed view on their structural physicochemical properties. 

TTus paper is concerned with the particular class of molecular sieves having periodic mesoporous structure with pore sizes in the range of 2 to 10 nm. They are comprised of the M41S mesoporous molecular sieves and solids with related structures. In the first part, the preparation methods and characterization techniques will be reviewed and discussed. Silicate-based materials and non-silicate materials will be dealt with separately. In the second part of this review particular emphasis will be put on potential applications reported in both the patent and the open literature. Early progress in tWs field has been presented in the previous Summer School by Casci [37]. Potential catalytic applications of M41S were also reviewed rprPTitlv 1381... 

The insertion of Ti in the zeolite framework was accompanied by a significant decrease in A1 content (Table 1). However, there was no stoichiometric process between A1 removal and Ti insertion. Moreover, it was found that the treatment of Ig of an aluminum containing beta zeolite with a 75 ml of 3 x 10 M oxalic acid solution decreased the Si/Al ratio from its original value of 30 to 85 due to A1 extraction. Attempts to incorporate Ti into other zeolites like ZSM-12 and mordenite were not successful. Interestingly, the extraction of A1 from these zeolite structures was also unsuccessful with oxalic acid solutions with comparable concentrations. However, preliminary data show that siliceous mesoporous molecular sieves (MCM-41 and HMS) treated similarly with ammonium titanyl oxalate solutions exhibit good epoxidation activity. It is inferred that the presence of framework cations that can be extracted by oxalate species and/or the presence of defect sites in the parent zeolite is a requisite for the subsequent incorporation of titanium. 

Many of the non-silica compositions showed problems with the stability and quality of the structure. Efforts to address these issues have been on going and quite successful in some cases such as all-alumina compositions (see below). Silica-based materials remain dominant as the most versatile and best quality molecular sieves (structure and stability) available by a facile synthesis. These attributes, especially the convenient synthesis made mesoporous silicate attractive for post-synthesis functionalization with other elements as well as organic moieties with active groups/ccnters. Recently the compositional diversity has been extended further to include both silica and organic moieties within the framework. The new class is referred to as periodic mesoporous organosilicas (PMOs). The synthesis involves surfactant-assisted assembly by hydrolysis of organo-silicon compounds. Additional discussion of the PMOs is presented below. 

The continuous effort of numerous academic and industrial laboratories around the world has resulted in recent years in successful synthesis of a number of new porous materials including new structural types of zeolites and zeolypes, siliceous and non-siliceous mesoporous molecular sieves, mesoporous zeolite single crystals, and micro/mesoporous or micro/macroporous composite materials of different chemical compositions. As a consequence of the success of basic research in this area, zeolites have found new industrial applications. 

The acidic properties of mesoporous molecular sieves rely on the presence of active sites in their framework. In the case of MCM-41 active sites are generated by the introduction of heteroatoms into the structure. In particular, Bronsted acid sites are introduced by isomorphous substitution of A1 for Si which is achieved by hydrothermal synthesis in which charged quaternary ammonium micelles are used as the template for charged alumino-silicate inorganic precursors. 

The second general formation mechanism for mesoporous molecular sieves involves the intercalation of surfactants into the layers of a layered silica, kanemite, followed by conversion into a hexagonal phase structure. This mechanism is therefore based on the intercalation of ammonium surfactant in kanemite, a type of hydrated sodium polysil-icate composed of single layered silica sheets. After the surfactants are ion exchanged into the layered structure, the silicate sheets are thought to fold around the surfactants and condense into a hexagonal mesostructure as shown in Fig. 6. 

The key property required of the inorganic species is ability to build up (polymerize) around the template molecules into a stable framework. As is already evident in this article, the most commonly used inorganic species are silicate ions, which yield a silica framework. The silica can be doped with a wide variety of other elements (heteroatoms), which are able to occupy positions within the framework. For example, addition of an aluminium source to the synthesis gel provides aluminosilicate ions and ultimately an aluminosilicate mesoporous molecular sieve. Other nonsilica metal oxides can also be used to construct stable mesoporous materials. These include alumina, zirconia, and titania. Metal oxide mesophases, of varying stability, have also been obtained from metals such as antimony (Sb), iron (Fe), zinc (Zn), lead (Pb), tungsten (W), molybdenum (M), niobium (Nb), tantalum (Ta), and manganese (Mn). The thermal stability, after template removal, and structural ordering of these mesostructured metal oxides, is far lower, however, than that of mesoporous silica. Other compositions that are possible include mesostructured metal sulfides (though these are unstable to template removal) and mesoporous metals (e.g., platinum, Pt). 

A number of literature reports dealt with Ga-modified mesoporous silicate molecular sieves [129,130,191,192]. Cheng et al. [191] synthesized Ga-MCM-41 with Si/Ga from 10 to 120. The quality of the samples was very sensitive to the pH of the gel mixture. No extraframework gallium was detected by Ga NMR in the as-synthesized samples. However, during calcination, the 4-coordinated gallium was partially expelled from the structure for samples with Si/Ga 20. Galloaluminosilicate [192] as well as Ti [193] ans manganese [194] modified mesoporous silicates were also synthesized and characterized. 

The incorporation of Ti into various framework zeolite structures has been a very active research area, particularly during the last 6 years, because it leads to potentially useful catalysts in the oxidation of various organic substrates with diluted hydrogen peroxide [1-7]. The zeolite structures, where Ti incorporation has been achieved are ZSM-5 (TS-1) [1], ZSM-11 (TS-2) [2] ZSM-48 [3] and beta [4]. Recently, mesoporous titanium silicates Ti-MCM-41 and Ti-HMS have also been reported [5]. TS-1 and TS-2 were found to be highly active and selective catalysts in various oxidation reactions [6,7]. All other Ti-modified zeolites and molecular sieves had limited but interesting catalytic activities. For example, Ti-ZSM-48 was found to be inactive in the hydroxylation of phenol [8]. Ti-MCM-41 and Ti-HMS catalyzed the oxidation of very bulky substrates like 2,6-di-tert-butylphenol, norbomylene and a-terpineol [5], but they were found to be inactive in the oxidation of alkanes [9a], primary amines [9b] and the ammoximation of carbonyl compounds [9a]. As for Ti-P, it was found to be active in the epoxidation of alkenes and the oxidation of alkanes and alcohols [10], even though the conversion of alkanes was very low. Davis et al. [11,12] also reported that Ti-P had limited oxidation and epoxidation activities. In a recent investigation, we found that Ti-P had a turnover number in the oxidation of propyl amine equal to one third that of TS-1 and TS-2 [9b]. As seen, often the difference in catalytic behaviors is not attributable to Ti sites accessibility. 

The characteristics of the mesoporous structure of our mono- and bimetallic molecular sieves are listed in Table 1. From this table, it can be concluded that the above described mesoporous silicates have heteroelements in the fi"amework. The unit cell parameter ao confirm incorporation of the metal cation in the fiumework of our materials. It is observed that for a defined metal and metal source, the unit cell parameter a increases with increasing the metal content and then decreases when the metal content is too high. As the bond length of M-O is higher than that of Si-0, the increase in unit cell parameter with increasing the metal content suggests the incorporation of metal ions in the fi amework of mesoporous structures. The loss in unit cell parameter observed when the metal content is too high is due to the loss, at least a part, of the mesoporous structure. The... 

Mesoporous alumino silicate molecular sieves with MCM-41 type structure synthesized using various A1 sources (i.e. aluminum sulphate, aluminum isopropoxide, pseudo boehomite and sodium aluminate) have been used as supports for Ni - Mo catalysts. The HDN of o-toluidine tmd cyclohexylamine was studied in a fixed bed flow reactor at 450°C and PH2 = 1 atm. The activity per unit of weight of the MCM - 41 supported catalysts was evaluated and compared to that of supported catalysts preptu ed by sequential impregnation method. The XRD and DRS data have been used to explain the observed trend in catalytic activity towards HDN reaction... 

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