Other Mesoporous Oxides

Mesoporous oxides from elements other than sihca have been reported as early as 1994. Cieslaetal. [169] found that metals such as Sb, Fe, Zn, Pb,W, and Mo also form mesoporous oxides. However, many of the mesophases obtained were lamellar and were not porous after template removal (calcination). Antonelli and Ying reported the transformation of titanium, niobium, and tantalum alkoxides into stable mesophases [170]. Subsequently, mesoporous oxides based on zirconium, hafnium, and manganese have been synthesized (for a recent review on these materials see [171]). Bagshaw and Pinnavaia [172] prepared mesoporous alumina with worm-like pores and a specific surface area of more than 400 m g . Mesoporous alumina with surface areas above 700 m g have been reported by Vaudry et al. [173]. 

For further details on the preparation of mesoporous siHcas and carbons, organic-inorganic hybrid materials (PMOs), and mesoporous thin films, the reader is referred to several reviews [179]. 

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The ER response of suspensions based on PANI/SBA nanocomposites has been also examined [101]. Its ER effect is much higher compared to PANI/MCM-41 nanocomposites due to higher PANI loading content. Besides silica mesoporous molecular sieves, other mesoporous oxide is also used to load PANI to form nanocomposites for ER fluid application [102]. 

Abstract A review of the thermolytic molecular precursor (TMP) method for the generation of multi-component oxide materials is presented. Various adaptations of the TMP method that allow for the preparation of a wide range of materials are described. Further, the generation of isolated catalytic centers (via grafting techniques) and mesoporous materials (via use of organic templates) is simimarized. The implications for syntheses of new catalysts, catalyst supports, nanoparticles, mesoporous oxides, and other novel materials are discussed. 

Although the idea of applying mesoporous thin films of Ti02 (or other suitable oxides) prepared by self-assembly strategies in combination... 

The majority of the titanium ions in titanosilicate molecular sieves in the dehydrated state are present in two types of structures, the framework tetrapodal and tripodal structures. The tetrapodal species dominate in TS-1 and Ti-beta, and the tripodals are more prevalent in Ti-MCM-41 and other mesoporous materials. The coordinatively unsaturated Ti ions in these structures exhibit Lewis acidity and strongly adsorb molecules such as H2O, NH3, H2O2, alkenes, etc. On interaction with H2O2, H2 + O2, or alkyl hydroperoxides, the Ti ions expand their coordination number to 5 or 6 and form side-on Ti-peroxo and superoxo complexes which catalyze the many oxidation reactions of NH3 and organic molecules. 

Ordered mesoporous materials of compositions other than silica or silica-alumina are also accessible. Employing the micelle templating route, several oxidic mesostructures have been made. Unfortunately, the pores of many such materials collapse upon template removal by calcination. The oxides in the pore walls are often not very well condensed or suffer from reciystallization of the oxides. In some cases, even changes of the oxidation state of the metals may play a role. Stabilization of the pore walls in post-synthesis results in a material that is rather stable toward calcination. By post-synthetic treatment with phosphoric acid, stable alumina, titania, and zirconia mesophases were obtained (see [27] and references therein). The phosphoric acid results in further condensation of the pore walls and the materials can be calcined with preservation of the pore system. Not only mesoporous oxidic materials but also phosphates, sulfides, and selenides can be obtained by surfactant templating. These materials have pore systems similar to OMS materials. 

The concept presented in Fig. 6 could use also other type of ordered mesoporous membranes, based on silica for example. As discussed before, oxides such as Ti02 provide better multi-functionalities for the design of such a type of nanofactory catalysts. Worth to note is that in the cover picture of the recent US DoE report Catalysis for Energy a very similar concept was reported. This cover picture illustrates the concept, in part speculative, that to selectively convert biomass-derived molecules to fuels and chemicals, it is necessary to insert a tailored sequence of enzyme, metal complexes on metal nanoparticles in a channel of a mesoporous oxide. 

Since mesoporous materials contain pores from 2 nm upwards, these materials are not restricted to the catalysis of small molecules only, as is the case for zeolites. Therefore, mesoporous materials have great potential in catalytic/separation technology applications in the fine chemical and pharmaceutical industries. The first mesoporous materials were pure silicates and aluminosilicates. More recently, the addition of key metallic or molecular species into or onto the siliceous mesoporous framework, and the synthesis of various other mesoporous transition metal oxide materials, has extended their applications to very diverse areas of technology. Potential uses for mesoporous smart materials in sensors, solar cells, nanoelectrodes, optical devices, batteries, fuel cells and electrochromic devices, amongst other applications, have been suggested in the literature.11 51... 

Two other mesoporous silicates, HMS and MSU-n, were prepared at room temperature in the presence of neutral amines, and polyethylene oxide surfactants, respectively. They have parallel cylindrical channels, but are not identical to MCM-41 [69,70,72]. The main structural difference is that the pore system of HMS and MSU-n silicates is much less ordered than that of MCM-41. 

The new method allows one to evaluate not only pore size distributions, but also specific surface areas, primary mesopore volumes and micropore volumes. Moreover, it is applicable in the micropore range and appears to be essentially free from artefacts produced by many other methods of micropore analysis. Thus, a new approach provides a versatile and convenient tool for characterization of MCM-41, silica-based porous materials and other mesoporous and/or microporous oxides. 

Block copolymers are valuable supramolecular templates for the synthesis of ordered large-pore mesoporous silica and other metal oxides because of their simple templating ability, low-cost commercial availability, and biodegradability. 

Since then, other colloidal oxide systems have been investigated in order to prepare ceramic mesoporous membranes designed for ultrafiltration. The preparation of an electronically conductive membrane from a Ru02 Ti02 mixed oxides sol and the application to an electro-ultrafiltration process [25,26], as well as the preparation of titania and zirconia ultrafiltration membranes [27], have been described following a colloidal process in which a partial destabilization of a metal oxide colloidal suspension is used to produce top layers with different pore size and pore volume in the mesoporous range. In agreement... 

A number of other photo-oxidations involving aromatic substrates have been reported, some of which again have been carried out in non-traditional reaction environments. A light-promoted oxidative cleavage of the olefinic bond in aromatic alkenes, which takes place in mesoporous Si02 (FSM 16) and involves a catalytic amount of I2, has been reported (Scheme 23). The photochemical involvement appears to extend no further than the formation of the iodine atoms. The suggestion that an a-iodoketone is an intermediate in the process is based on NMR evidence from the reaction where R = Bu, but it is not clear how this intermediate is converted to the final product. A similar transformation of aromatic alkenes has been carried out in zeolite NaY. Irradiation of styrene,... 

In summary, highly cubic ordered cobalt oxides with crystalline walls have been synthesized by an accurately controlled incipient wetness approach using mesoporous silica as hard template and cobalt nitrate as the precursors. Compared with the previously reported solution impregnation processes, this technique is facile, time-saving and economical. This technique can be used to synthesize ordered mesoporous metal oxides, and we expect that rvith this approach various kinds of mesoporous oxides or other materials can be synthesized, which may benefits their applications in many areas such as in catalysis, sensors, clean energy and electronics. 

Iron modified zeolites and ordered mesoporous oxides have been studied as catalysts for the sulfur dioxide oxidation in sulfur rich gases. Both zeolitic materials and mesoporous oxides show very good activity in this reaction. Other than solid state or incipient wetness loaded MCM-41 materials, the zeolites do not show an initial loss of activity. However, they loose activity upon prolonged exposure to reaction conditions around 700°C. The zeolitic samples were analyzed via X-ray absorption spectroscopy, and the deactivation could be related to removal of iron from framework sites to result in the formation of hematite-like species. If the iron can be stabilized in the framework, these materials could be an interesting alternative to other iron based catalysts for the commercial application in sulfur rich gases. 

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