Pore mesostructure

Several synthetic strategies to control the sizes of mesoporous nanoparticles have been reported. Lu[272] reported a rapid, aerosol-based process for synthesizing solid, well ordered spherical particles with stable pore mesostructures of hexagonal and cubic topology, as well as layered (vesicular) structures. This method relies on evaporation-induced interfacial self-assembly confined to spherical aerosol droplets. This simple, generalizable process can be modified for the formation of ordered mesostructured thin films. 

For instance, delaminated zeolite ITQ-6 (delaminated FER material),when properly modified with aminopropyl groups, showed a higher efficiency for CO2 capture than large-pore mesostructured materials modified with the same amount of amine groups [51]. 

Fig. 11 Pore size distributions and TEM images of ZrOi 4Si02 materials formed from Zr[OSi(O Bu)3]4. The upper portion shows a xerogel and the bottom portion shows a mesostructured material...

Pt particles remain highly dispersed in the reaction mixture during mesostructure formation. All measurements including XRD, SAXS, and TEM indicate a well-ordered silica structure. N2 physisorption measurement indicated high surface areas (523-661 m g ) and meso-sized pores (112-113 A) for the silica supports produced in the presence of different Pt particles. 

Figure 4.18 TEM images showing the mesostructures of Ti02 species dispersed in Si02 transparent thin films with (a) a hexagonal ordered pore arrangement and (b, c) cubic symmet7. Reproduced from [247] (2003) with permission from Elsevier.

Mesostructured materials with adjustable porous networks have shown a considerable potential in heterogeneous catalysis, separation processes and novel applications in optics and electronics [1], The pore diameter (typically from 2 to 30 nm), the wall thickness and the network topology (2D hexagonal or 3D cubic symmetry) are the major parameters that will dictate the range of possible applications. Therefore, detailed information about the formation mechanism of these mesostructured phases is required to achieve a fine-tuning of the structural characteristics of the final porous samples. 

Similarly, Hg(n) binding to thiol-functionalized mesoporous silica for which effective access to all the binding sites (100% of SH groups com-plexed with Hg(n) was achieved in micelle-templated mesostructures with pore diameters larger than 2.0 nm, whereas incomplete filling was always observed with corresponding amorphous silica-based adsorbents.37... 

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 N2 adsorption-desorption isotherms for MSU-Ge-2 show a type-lV adsorption branch associated with a well-defined capillary condensation step at P/Po 0.13, characteristic of uniform mesopores (Fig. 4). The adsorption data indicate a very high Brunauer-Emmett-Teller (BET) surface area of 363 m /g and a pore volume of 0.23 cm /g. Given that the Ge mesostructure is much heavier than the corresponding silica, this surface area is actually equivalent to silica with a surface area of 1,316 m /g. 

Fig. 8 Kubelka-Munk optical absorption spectra of as-prepared mesostructured (black) and mesoporous NU-Ge-1 (red) semiconductors and NU-Ge-1 incorporating into the pores TCNE (blue) and TTF (green line) organic molecules. The recovered optical adsorption spectra of NU-Ge-1 by encapsulation of TCNE-TTF complexes are also given (dashed lines). Inset optical absorption spectrum of NU-Ge-1 encapsulating anthracene...

As indicated by XRD patterns, there exist just 2-3 broad peaks in the calcined acid-made materials (Fig. 3A). Moreover, the N2 adsorption/desorption isotherm shown in Fig. 3B, the calcined acid-made mesoporous silica indeed possesses a broad capillary condensation at the partial pressure p/p0 of ca. 0.2-0.4, indicating a broad pore size distribution with a FWHM ca. 1.0 nm calculated from the BJH method. This is attributed to the occurrence of partial collapse of the mesostructure during the high temperature calcination. The hexagonal structure completely collapsed when subjected to further hydrothermal treatment in water at 100 °C for 3 h. Mesoporous silica materials synthesized from the acid route are commonly believed to be less stable than those from the alkaline route [6,7]. 

To improve the meso-structural order and stability of the mesoporous silica ropes, a postsynthesis ammonia hydrothermal treatment (at 100 °C) was invoked. As indicated by the XRD profile in Fig. 3A, 4-5, sharp features are readily observed in ammonia hydrothermal treated samples. Moreover, after the post-synthesis ammonia treatment, the sample also possesses a sharp capillary condensation at p/po 0.35(Fig. 3B) corresponding to a much narrower BJH pore size distribution of ca. 0.12 nm (at FWHM). In other words, the mesostructures are not only more uniform but also more stable when subjected to the post-synthesis treatment. The morphology of the silica ropes remained unchanged during the ammonia hydrothermal process. The mesostructures remain intact under hydrothermal at 100 °C in water even for extended reaction time (> 12 h). 

MCM-41 samples with increased hydrothermal stability could be successfully synthesized by adding additional salts like tetraalkylammonium bromide or sodium bromide to the synthesis gel. The increased stability is related to the increased condensation of the silanol groups during the formation of the mesostructure. Hydrothermally stable MCM-41 structures with different pore diameter can also be synthesized by this method using surfactants with varied chain length. 

A novel mesoporous intercalate belonging to the class of mesostructured solid acids known as porous clay heterostructures (PCH) has been synthesized through the surfactant - directed assembly of silica in the two - dimensional galleries of saponite. The new saponite PCH, denoted SAP-PCH, exhibits a basal spacing of 32.9 A, a BET surface area of 850 m2/g and pore volume of 0.46 cm3/g. SAP-PCH is an effective catalyst for the condensed phase Friedel-Crafts alkylation of bulky 2,4-di-tert-butylphenol (DBP) with cinnamyl alcohol to produce a large flavan, namely, 6,8-di-tert-butyl-2,3-dihydro[4H]benzopyran. 

Mesostructured molecular sieves such as MCM-41 ( 1,2 ), because of their easily accessible mesoporosity, acidity, thermal stability to 800°C, and pore diameter in the 2 to 10 nm range could prove particularly useful in the preparation of novel catalysts and... 

Mesostructured materials are granules containing individual platelets (crystals) associated in a fairly random manner. This type of configuration is always associated with a bi-porous structure, in which small particles (platelets) have pores, usually mesopores, different from the composite particle (secondary mesopores and macropores). The secondary pore structure controls access to the individual crystal mesoporosity. As a result, different mass transfer resistances to diffusion through bi-porous structures could be present. In order to evaluate the relative significance of both primary and secondary pore diffusion, usually two different particle sizes are employed in diffusion measurements. 

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